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ARTICLE IN PRESS

Progress in Energy and Combustion Science 34 (2008) 351–376


www.elsevier.com/locate/pecs

Thermodynamic irreversibilities and exergy balance


in combustion processes
S.K. Soma,, A. Dattab
a
Department of Mechanical Engineering, Indian Institute of Technology, Kharagpur 721 302, India
b
Department of Power Engineering, Jadavpur University, Salt Lake Campus, Kolkata 700 098, India
Received 30 March 2007; accepted 4 September 2007
Available online 23 October 2007

Abstract

The growing concern for energy, economy and environment calls for an efficient utilization of natural energy resources in developing
useful work. An important thermodynamic aspect in gauging the overall energy economy of any physical process is the combined energy
and exergy analysis from the identification of process irreversibilities. The present paper makes a comprehensive review pertaining to
fundamental studies on thermodynamic irreversibility and exergy analysis in the processes of combustion of gaseous, liquid and solid
fuels. The need for such investigations in the context of combustion processes in practice is first stressed upon and then the various
approaches of exergy analysis and the results arrived at by different research workers in the field have been discussed. It has been
recognized that, in almost all situations, the major source of irreversibilities is the internal thermal energy exchange associated with high-
temperature gradients caused by heat release in combustion reactions. The primary way of keeping the exergy destruction in a
combustion process within a reasonable limit is to reduce the irreversibility in heat conduction through proper control of physical
processes and chemical reactions resulting in a high value of flame temperature but lower values of temperature gradients within the
system. The optimum operating condition in this context can be determined from the parametric studies on combustion irreversibilities
with operating parameters in different types of flames.
r 2007 Elsevier Ltd. All rights reserved.

Keywords: Combustion; Chemical reaction; Transport processes; Exergy; Irreversibility

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2. Basic concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
2.1. Exergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
2.2. Irreversibility and its causes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
2.3. Exergetic efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
3. Exergy analysis approach in combustion systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
3.1. Different combustion systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
3.2. Physical processes in a combustion system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
3.3. Exergetic performance analysis based on exergy balance: approach 1. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
3.3.1. Equilibrium approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
3.3.2. Analysis in well-stirred reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
3.3.3. Intrinsic analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
3.4. Exergetic performance analysis using entropy generation equation: approach 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . 359

Corresponding author. Tel.: +91 3222 282978; fax: +91 3222 282278.
E-mail address: sksom@mech.iitkgp.ernet.in (S.K. Som).

0360-1285/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pecs.2007.09.001
ARTICLE IN PRESS
352 S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376

4. State of art in exergy analysis in combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360


4.1. Gaseous fuel combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
4.2. Liquid fuel combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
4.2.1. Droplet exergy models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
4.2.2. Spray exergy models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
4.3. Solid fuel combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 375

1. Introduction The conventional definition of combustion efficiency,


however, does not pay any attention to the quality at
The world energy consumption is largely dependent on which the thermal energy from the combustor is available
fossil fuels even today where combustion plays a key role in in the hot products of combustion. For example,
the energy utilization process. Combustion of fuel finds its if we consider combustion of a fuel with air at atmospheric
importance in heating, power production, transportation temperature in a well-stirred combustor, the final tempera-
and process industries. The energy-intensive industries like ture of the product upon complete combustion of
petroleum refining, steel, chemical, glass, metal casting, the fuel will depend on the extent of the air supplied. An
aluminum, etc. are also heavily dependent on combustion increase in the excess air will lower the product gas
processes. In 2003, almost 86% of a total 421 quadrillion kJ temperature, even when the energy content of the gas
energy produced from the primary energy resources came remains the same in consideration of adiabatic walls
from the combustion sources [1]. In this, the shares of oil, of the combustor. Thus, the work producing potential
natural gas and coal, which are the three principal pillars of the product gas decreases, as given by the second
for energy supply, were 162, 99 and 100.5 quadrillion kJ, law of thermodynamics. So complete conversion of
respectively. The high share of combustion associated energy in the combustor cannot be its sole performance
energy production is maintained in all the four major indicator.
energy utilization sectors, viz. residential, commercial, Probably the most important use of combustion in
industrial and transportation. This trend is believed to practice is for the production of work. The transportation
continue in the coming years. A projection of data to 2030 sector and the electricity generating plants use the energy
shows a 71% increase in the total energy consumption obtained from combustion for the generation of work.
figure from that in 2003. However, the share of fossil fuel- Many applications in the process industries also employ
based resources has been predicted to remain at the same combustors for the purpose of getting work. In all these
range of 86% as is in 2003. Despite the on-going depletion applications, the work producing potential of the products
in the fossil fuel reserves and the ever-increasing concern of combustion should be the performance indicator for the
towards the conservation of the environment, the growth in combustion process. Exergy is the term coined [2] to
the use of oil in the time span of 2003–2030 has been describe the work producing potential of energy, and
envisaged to be 47.5%, that in natural gas to be 91.6% and hence, an exergy-based analysis of combustors should find
in coal to be 94.7%. The figures reveal that the combustion importance in optimizing the design.
system and combustors will maintain their importance in Many works are available in the literature advocating
the energy sector in the next several decades to come. the importance of exergy-based analysis for the perfor-
On this backdrop, the question of efficient operation of mance evaluation of thermodynamic systems [3–5].
the combustors finds importance. Both the limited com- According to them, energy-based performance analysis
bustible fossil fuel reserve and the damage that combustion are often misleading as they fail to identify the deviation
causes to the environment, e.g. through the liberation of from ideality. An ideal process is reversible and does
the GHGs, calls for an increase in efficiency of the system not incur any destruction of exergy. The practical
through the minimization of the losses. In a gross sense, the processes generate thermodynamic irreversibilities internal
efficiency of a device whose primary purpose is the to them and result in a loss of exergy even when there
conversion of energy is given by the ratio of the energy is no loss of energy external to the system. Several studies
in the converted form to that before conversion. In a have indicated that the conventional combustion process
combustor, the chemical energy of the fuel is converted involves inherent thermodynamic irreversibility, which
into thermal energy. Therefore, the conventional definition significantly limits the conversion of fuel energy into
of efficiency of a combustor indicates how much thermal work [6]. For typical atmospheric combustion systems,
energy is available for use from the stored chemical energy about 1/3rd of the fuel exergy becomes unavailable
of the fuel. The losses in a combustor that accounts for the due to the inherent irreversibilities in the combustor. Most
decrease in the efficiency are due to unburnt fuel, of this irreversibility is associated with the internal
incomplete combustion and heat loss to the surrounding heat transfer within the combustor between the products
across the combustor wall. and reactants. Such heat transfer becomes inevitable in
ARTICLE IN PRESS
S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376 353

Nomenclature uofl adiabatic laminar flame speed (m/s)


V volume (m3)
A area (m2) v specific volume (m3/kg)
A_ rate of exergy flow (J/s)
a specific exergy (J/kg) Greek letters
ach specific chemical exergy (J/kg)
B transfer number a thermal diffusivity (m2/s)
Ck mass fraction of species k w chemical potential (J/kg)
cp specific heat (J/kg K) dij Kronecker delta
f ki body force per unit mass on species k (N/kg) f equivalence ratio
h specific enthalpy (J/kg) j overall potential energy of all species (J/kg)
I_ rate of exergy destruction (J/s) ZII exergetic efficiency
j ki mole flux of species k (kmol/m2 s) m viscosity (kg/m s)
K specific kinetic energy (J/kg) r density (kg/m3)
k thermal conductivity (W/m K) tij stress tensor (N/m2)
M molecular weight _k
o volumetric rate of formation of species k
m _ mass flow rate (kg/s) (kg/m3 s)
m _ 000 volumetric rate of mass generation (kg/m3 s)
Pr Prandtl number Subscripts
p pressure (N/m2)
Q_ rate of heat transfer (W) a air
q_ i conduction heat flux vector (W/m2) cv control volume
R̄ universal gas constant (J/kmol K) ex exit
Re Reynolds number f fuel
S_ g rate of entropy generation (W/K) k species index
s specific entropy (J/kg K) in inlet
s_000
g volumetric entropy generation rate (W/m3 K) r exergy reference environment
T temperature (K)
t time (s) Superscripts
U ki diffusion velocity of species k (m/s)
u specific intermolecular energy (J/kg) ex exit
ui velocity vector (m/s) in inlet

both premixed and diffusion flames, where highly energetic proach and minimization of entropy generation approach.
product molecules are free to exchange energy with The concept of minimizing the irreversible production of
unreacted fuel and air molecules. Fig. 1 depicts how entropy is inherent in reducing the exergy loss in a process
entropy is generated due to internal heat transfer in a
hydrogen–oxygen reaction. However, the entropy genera-
tion in a combustion process is attributed to both internal Tcool Tmax Tadiabatic
heat and mass transfers and chemical reactions. Internal
heat transfer within the combustor is often difficult to be O H H
recognized as an issue affecting the performance, because it O O
O O
does not result in a direct energy loss from the combustion H H H
zone to the surrounding. Instead, internal heat transfer H
H H
H H
only degrades the exergy of the product flue gas and O H H
H O
reduces its work potential. Therefore, the actual energy O
O O
penalty does not become apparent until the work genera- O H H H
H O
tion step, which is separated from the combustion step, is H H O
H O H H
taken into account. H H
H
O
The losses due to process irreversibilities can be H O
calculated using the second-law analysis, either from the
unbalanced rate of exergy input or from the rate of entropy Flame Front
generation. Accordingly two different approaches for Fig. 1. Schematic of how entropy is generated in H2–O2 flame front due to
second-law-based process performance evaluation and internal heat transfer. Energetic product molecules dissipate its energy in
optimization studies have evolved—exergy analysis ap- collision with surrounding cool reactant molecules. After Daw et al. [73].
ARTICLE IN PRESS
354 S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376

for improving the efficiency. Accordingly, the most efficient 2. Basic concepts
performance is achieved when the exergy loss in the process
is the minimum. Both the approaches find wide accept- 2.1. Exergy
ability in heat transfer engineering, e.g. in the optimization
of heat exchangers, fins, thermal insulation, electronic The concept of exergy is a direct outcome of second law
package cooling, etc. and have been chronologically of thermodynamics. The exergy of a system is defined to be
reviewed in many references [7–11]. its work potential with reference to a prescribed environ-
Yilmaz et al. [12] presented an exhaustive review of the ment known as ‘exergy reference environment’. The term
application of various second-law-based analyses for the ‘work potential’ implies physically the maximum theore-
optimal design of heat exchangers. They described the need tical work obtainable if the system of interest and the
for the systematic design of heat exchangers using second- prescribed environment interact with each other and reach
law-based procedure. Accordingly, the design of heat the equilibrium. The term exergy is sometimes referred by
exchangers based on low first cost approach dictating the thermodynamically synonymous term ‘availability’ and is a
minimum size leads to higher irreversibilities, as it requires composite property of the system and the reference
a larger temperature difference between the streams to environment. In general, the specific exergy is defined as
affect the heat transfer. Such designs are inefficient from a ¼ K þ j þ ðu  ur Þ þ pr ðv  vr Þ  T r ðs  sr Þ þ ach , (1)
the exergy standpoint, as they do not preserve the quality
of energy during the transformation. The authors pro- where K is the specific kinetic energy of the system and j is
claimed that the exergy-based performance evaluation is the potential energy per unit mass due to the presence of any
worthy as it gives a measure of the perfection of the conservative force field. T, p, u, v and s are the temperature,
thermal process. pressure, specific intermolecular energy, specific volume and
Historically, second-law-based analysis was developed to specific entropy, respectively, while ach represents the specific
evaluate the process of power generation from heat. chemical exergy. The terms with the subscript r are the
Applications of exergy analysis for the performance properties of the exergy reference environment.
evaluation of power-producing cycles have increased in
the recent years. A lot of works are now available in the 2.2. Irreversibility and its causes
literature where the second-law-based analyses have been
applied for optimizing performance on coal-based electri- Any natural process depletes the total exergy of all
city generation using conventional [13–19], fluidized bed interacting systems in the process (i.e. the exergy reserve of
and combined cycle technology [20] as well as for gas the universe decreases). This is known as law of degradation
turbine [21–24], internal combustion engine [25–32] and of energy. The destruction of exergy is termed as irreversi-
blast furnace [33] applications. It can be concluded from all bility, which is considered to be a thermodynamic character-
these studies that in power plants involving combustion, istic of a physical process. All natural processes are
the major part of the exergy loss takes place in the process irreversible. The causes of irreversibility lie in the basic
of combustion. requirement of a natural process to occur and can be
Lior [34] and Lior et al. [35] outlined the necessity of classified broadly as: (i) lack of thermodynamic equilibrium
second-law-based analysis of combustion processes with and (ii) dissipative effects associated with a natural process.
the following objectives: The thermodynamic irreversibility in a process is character-
ized by the entropy generation in the process. For continuous
(1) identification of the specific phenomena/processes that processes performed by a system, it can be written that
have large exergy losses or irreversibilities,
I_ ¼ T r S_ g , (2)
(2) understanding of why these losses occur,
(3) evaluation of how they change with the changes in the where I_ is the rate of exergy destruction or dissipation and S_ g
process parameters and configuration, and is the rate of entropy generation. Eq. (2) is known as the
(4) as a consequence of all the above, suggestions on how Gouy–Stodola equation [8].
the process could be improved. An engineering system, in general, involves a number of
coupled physical processes. The entropy generation due to
The present review will throw light on the state of art all these processes together determines the system irrever-
knowledge on thermodynamic irreversibility and exergy sibility. The general expression for entropy generation in a
loss that occur in fundamental physical processes in the continuous field described by a system is derived from the
combustion of solid, liquid and gaseous fuels. The different equation of change of entropy (entropy transport equa-
approaches adopted by the researchers to achieve the goal tion). This is discussed in Section 3.4.
have been reviewed with their relative merits and demerits.
A final conclusion has been drawn to give direction on 2.3. Exergetic efficiency
future research needed for more efficient utilization of
fuel’s useful energy through a trade-off between the energy The parameter that gauges the effectiveness of a system
and exergy-based efficiencies. in preserving its exergy in performing a physical process is
ARTICLE IN PRESS
S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376 355

Q One way of distinguishing the combustion behavior in


. . practical systems is based on the fuel that is burnt. Though
Ain Aex the major share of the fuels used for combustion is the
Reactants Combustion System
Products hydrocarbons, the composition of the fuel differs and
Inlet Outlet accordingly the fuel can be either in the gaseous, liquid or
solid phase. The gaseous fuels can homogeneously mix
Fig. 2. Schematic of a combustion system showing the exergy transfer.
with the oxidizer very easily for burning. The need of fuel
preparation is the minimum and the combustion reaction
known as exergetic efficiency. This is also called as second- proceeds rapidly with little formation of the polluting
law efficiency. Lower is the irreversibility, higher is the species. However, the cost of the fuel is high and the
exergetic efficiency and vice versa. In determining the storage and handling systems are voluminous and elabo-
exergetic efficiency of a process performed by a system, one rate. The convenient burning of the gaseous fuels mostly
has to consider the exergy quantities that cross the system pertains to small combustion applications including the
boundaries either as flow exergy associated with mass flux, domestic use. However, the present day concern of the
or as exergy transfer built in with the transfer of energy environment calls for the use of gaseous fuels even in large
quantities (heat and work). combustors to keep the emission levels within the statutory
A combustion system in general performs a number of limits. The solid fuels are suitably gasified to obtain
coupled transport processes like convection and diffusion synthetic gas and liquid fuels are pre-vaporized and
of mass, momentum and energy along with the process of premixed with air to get a lean vapor–air mixture in the
chemical reactions. All of them can be realized either in a gas phase for burning.
laminar or in a turbulent flow regime. In both cases, the The liquid fuel burning is mainly promoted in the
expression for exergetic (or second law) efficiency of a transportation sector for its easy storage and relatively
combustion system (see Fig. 2) can be written as clean handling. Various forms of liquid hydrocarbon fuels
are used in automobile engines, diesel engines, aircraft gas
A_ ex
ZII ¼ , (3) turbines, etc. The heavier fractions of the liquid hydro-
_ _
Ain  Qð1  ðT r =TÞÞ carbons, which are relatively less expensive, are used in
where A_ in and A_ ex are the rate of flow availability at inlet furnaces and boilers. The fuel preparation is necessary for
and exit to the combustor, respectively. Q_ is the rate of heat the high viscous species, where heating is required to
loss from the combustion system and T is the representa- control the fuel viscosity for reducing the pumping power
tive temperature at the boundary surface of combustor. and for better atomization. The atomization of the liquid
From an exergy balance, we can write into minute droplets is always necessary to enhance the
  evaporation process, which precedes the combustion.
Tr
I_ ¼ A_ in  A_ ex  Q_ 1  . (4) Different types of atomizers are used depending upon the
T application. Combustion of liquid fuel sprays is an intricate
Hence, it becomes affair involving various inter-related phenomena, like
atomization, penetration, evaporation, interference, mixing
I_ and chemical reaction. Multi-component nature of most of
ZII ¼ 1  . (5)
_  ðT r =TÞÞ
A_ in  Qð1 the practical fuels further complicates the situation.
Solid fuel burning is always heterogeneous in nature
occurring at the surface of the fuel and inside the pores
For an adiabatic combustor (Q_ ¼ 0): when the fuel particles are porous. Mainly coal, lignite and
A_ ex I_ biomass fuels come under this category. These fuels require
ZII ¼ ¼1 . (6) an elaborate fuel preparation process, e.g. in case of
_
Ain _
Ain
pulverized coal-fired boiler the fuel is required to be
pulverized from the coarse size to fine powder having mean
size of 50–75 mm. The utility boilers and heat treatment
3. Exergy analysis approach in combustion systems furnaces are the two major applications using solid fuels.

3.1. Different combustion systems 3.2. Physical processes in a combustion system

In the practical world, combustion is used in various A number of coupled interacting physical processes take
devices from the simplest one like a candle to the most place in a combustion system to initiate and sustain the
complex ones like rocket and scramjet engines. However, combustion reactions. The primary requirement for a
there are fundamental differences in the physical processes combustion reaction is the mixing of fuel and oxidizer so
involved in combustion in different devices in more than that they come in contact at the molecular level. Except for
one aspect. Borman and Ragland [36] cited and analyzed solid fuel combustion, all combustion reactions take place
examples of combustion in many important devices. in the gaseous phase. Therefore, for liquid fuel combustion,
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vaporization of fuel and its mixing with the air (oxidizer) One major process in a combustion system is the chemical
are the controlling processes in sustaining the combustion reaction. The word combustion is usually defined in its
reactions. A combustion system, in general, is a multi- simplest form as the rapid oxidation reaction generating
component and multiphase system. The physical processes heat or both heat and light. The definition itself emphasizes
occurring in the system can be classified broadly in two the intrinsic importance of chemical reactions to combus-
groups, namely: (i) transport processes and (ii) chemical tion. The oxidation between fuel and oxidizer in a
reactions. The transport processes pertain to the transport combustion system takes place through a number of
of mass momentum and energy, which involve the reaction steps involving the production of intermediate
processes of diffusion and convection of those quantities. species in the form of compounds, elements, radicals,
The turbulence plays an additional key role by transporting molecules and atoms. The number and details of the steps
mass momentum and energy through turbulent eddies for a given reaction is provided by the combustion
along with the transport of the quantities through chemistry. A detailed reaction mechanism involving inter-
molecular diffusion and flow-aided convection. The phy- mediate reaction steps is very complex and the combustion
sical aspects of transport processes are governed by three chemistry of many reactions is not fully understood even
basic conservation equations as follows: today. The use of global or quasi-global reactions to express
the combustion chemistry is a ‘black box’ approach, since it
does not provide a basis for understanding what actually
Mass conservation equation of individual species:
happens chemically in the system. However, for oxidation of
qC k q   hydrocarbon fuels, particularly of higher paraffin or alkane
þ _ k,
rC k uj þ rC k U k;j ¼ o (7)
qt qxj group, global or quasi-global steps can capture the overall
where Ck is the mass fraction of the species k in the behavior of the reaction processes, and may be used for
mixture, and uj and Uk,j are the mass average velocity and engineering approximations with due regard to their
the mass diffusion velocity for the species k, respectively. limitations. Westbrook and Dryer [37] present and evaluate
o_ k is the rate of formation of the kth species. In a general one-step, two-step and multi-step global kinetics for a wide
multicomponent system comprising N components, there variety of hydrocarbon oxidations. The chemical reactions
are N equations of this kind. The addition of these N for gaseous and liquid fuel combustions are referred to as
equations gives the equation for conservation of bulk mass homogeneous reactions, which take place in gas phase as a
and is known as the continuity equation. result of the collisions of gas-phase molecules of the reacting
species (fuel and oxidizer). Therefore, the primary step in
liquid fuel combustion is the vaporization of liquid fuel. On
Momentum conservation equation: the other hand, the solid fuel combustion involves hetero-
q q   qp qtji geneous reactions, where gas-phase oxidizer reacts with
ðrui Þ þ ruj ui ¼  þ , solid-phase fuel at the surface of the solid fuel. The rate of
qt qxj qxj qxj
! any chemical reaction is guided either by the kinetics of the
X
N
þr C k f ki . ð8Þ reaction or by the rate of diffusive transport of the reacting
k¼1 molecules to come in contact for possible collision for
reaction. The rate equation of either kinetic-controlled or
Energy conservation equation:
diffusion-controlled reactions are developed with the help
q q   qp qp qui of the physics of the governing process, and involve
ðrhÞ þ ruj h ¼ þ uj þ tij
qt qxj qt qxj qxj empirical model parameters, which are tuned to the best
qq_ j q X N agreement with the actual reaction rates found from
  rC k U k;j experiments.
qxj qxj k¼1
! The direction of a chemical reaction is provided by the
XN second law of thermodynamics, and is determined by the
 hk þ r C k f k;j U k;j . ð9Þ difference between the sum of the products of chemical
k¼1
potential and stoichiometric coefficient of the reacting
There are numerous physical models and approaches species and that of the product species. Similar to transport
followed by several computational methods to solve the processes, thermodynamic irreversibility is incurred by a
above equations in determining the velocity, temperature chemical reaction and is determined by the chemical
and species concentration fields in a combustion system. affinity (potential driving the chemical reaction) and the
The field variables define the thermodynamic potentials for specific rate of the reaction.
respective diffusive and convective fluxes of mass momen-
tum and energy. The rate equations of the fluxes are given 3.3. Exergetic performance analysis based on exergy
by the phenomenological laws of respective processes. The balance: approach 1
transport processes are inherently irreversible due to
thermodynamic dissipation in the processes occurring One way of analyzing the performance of a combustor is
under a finite potential gradient. by the exergy balance across the combustor. Considering
ARTICLE IN PRESS
S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376 357

the fuel and air entering the combustor either separately, or The specific exergy of the fuel stream may comprise both
in the form of a mixture, it is possible to calculate the the thermomechanical and chemical exergy components.
exergy flow rate at the inlet to the combustor. It will The thermomechanical component is calculated as above
comprise the chemical exergy of the fuel and the thermo- considering the corresponding properties and state of the
mechanical (or physical) exergy of the fuel and air. The fuel instead of air and assuming the fuel as an ideal gas.
combustion analysis in the combustor results in the The chemical exergy component depends upon the type of
product stream at a particular pressure, temperature and fuel and is based on stoichiometric reaction of complete
composition, from which the exergy of the outlet stream is combustion of the fuel and a reference state of concentra-
evaluated. The accuracy of the result depends upon the tion of the constituent products [38].
accuracy of the combustion analysis performed by the The chemical reaction of the fuel with air is considered
models with different degrees of complexity. through single-step global reaction chemistry as follows,
when there is sufficient supply of air for complete
combustion
3.3.1. Equilibrium approach
The simplest method of calculation considers a zero- 2
CH4 þ ðO2 þ 3:76N2 Þ ! CO2 þ 2H2 O
dimensional model with the product stream leaving as an f
equilibrium mixture of all the product species at a single  
2 2
pressure and temperature. The analysis adopts the laws of þ  2 O2 þ  3:76N2 . ð14Þ
f f
thermochemistry, without considering specific transport
and kinetic rates. In other words, both the transport and In Eq. (14), f represents the equivalence ratio, which has to
chemistry are assumed to be infinitely fast. Such a method be less than or equal to unity to ensure sufficient air for
is widely used in all thermodynamic analyses of cycles and complete reaction.
systems involving a combustor. In case of insufficient air, it may be assumed that the
Let us consider, as an example, a simplified adiabatic, oxygen of air preferentially reacts with hydrogen of the fuel
well-stirred combustor burning a stream of fuel (methane to form the water. The oxygen then converts the carbon to
(CH4)) in air. The rate of exergy flow at the inlet is carbon monoxide, a part of which is converted to carbon
associated with the inflow of air and fuel to the system and dioxide depending upon the availability of oxygen. The
can be written as above assumption for writing the stoichiometric chemical
equation is logical since the relative affinities of hydrogen,
A_ in ¼ m
_ a ain _ f ain
a þm f , (10) carbon and carbon monoxide for oxygen are in that
_ a and m_ f are the mass flow rates of air and fuel, respective order. The reaction can therefore be expressed as
where m
 
respectively, into the combustor and ain in
a and af are the 2 4
specific exergy of air and fuel at the inlet. In consideration CH4 þ ðO2 þ 3:76N2 Þ !  3 CO2
f f
of air as an ideal gas, the specific flow exergy of air,  
4 2
considering only the thermomechanical contribution, is þ 4 CO þ 2H2 O þ  3:76N2 . ð15Þ
f f
determined from the following equation:
 in   in  As the combustor is adiabatic, there is no energy transfer
ain
a ¼ ha  hr  T r s a  s r . (11)
across it. The energy equation therefore gives the product
In the equation, h and s refer to the specific enthalpy and gas temperature at the combustor exit (Tex) as the adiabatic
specific entropy, respectively, with the subscript a referring flame temperature considering the variation of the specific
to air and r referring to the exergy reference environment. heat of the product components with temperature. The
The superscript in refers to the inlet condition. exergy flow rate at the exit to the combustor is evaluated as
The terms on the right-hand side can be evaluated as X  ex   
A_ ex ¼ _ ex
m k hk  hr  T r S ex
k  sr , (16)
Z T ina
 in  k
ha  h r ¼ cpa ðTÞ dT, (12)
Tr where k is the index for each species present in the product
stream at the exit. The exit properties (temperature and
and
pressure) are used for evaluating the Eq. (16).
Z T in Z pin The exergetic efficiency of combustion is then given as in
  a cpa ðTÞ R̄ a dp
sin
a  sr ¼ dT  . (13) Eq. (6), i.e. ZII ¼ A_ ex =A_ in . Fig. 3 shows the variation of the
Tr T Ma pr p
exergetic efficiency, calculated using the above formula-
In the above equations, cpa ðTÞ is the specific heat of air as tion, with the equivalence ratio and inlet air temperature.
a function of temperature, R̄ and Ma are the universal gas The fuel is considered to enter the combustor at a
constant and the molecular weight of air, respectively. T in a temperature of 298 K and the combustor operates at
and pina are the temperature and pressure of air at the inlet, 1 atm pressure. The results show that the second-law
while Tr and pr are the exergy reference temperature and efficiency is the maximum for the stoichiometric supply of
pressure, respectively. air. The lower product gas temperature at the exit for
ARTICLE IN PRESS
358 S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376

1 Well - stirred Reactors


300 K
450 K
0.9 600 K
750 K Reactant Product
900 K in out
Exergetic Efficiency

0.8

0.7

0.6

0.5 . .
m m
Tin . Tex
0.4 mi′′′
Ci, in Ci, ex
0.4 0.6 0.8 1 1.2 1.4 . .
Ain Aex
Equivalence Ratio

Fig. 3. Variation of exergetic efficiency with equivalence ratio of the


reactant mixture at different inlet air temperature calculated with the Fig. 4. Analysis in a well-stirred reactor model: Entire combustor is
equilibrium approach. divided into a number of well-stirred reactors.

a lean mixture as a result of the excess air supply reduces increases the rate of transport and such an assumption may
the second-law efficiency of the combustor. This is despite often be acceptable. The reaction speed is determined using
the fact that all the energy stored in the fuel is contained in the kinetic parameters of the reactions for the assumed
the product gas with the complete combustion of the fuel in reaction scheme. Depending on the size of the combustor,
case of a lean fuel–air mixture in the adiabatic combustor. the entire combustor may be assumed as a single well-
Therefore, it is clear that neither the completeness of stirred reactor. Otherwise, if the size is large, it can be
combustion nor the energy content of the product gas divided into several such reactors in series, with the outlet
determines the exergy-based performance of the combus- of one entering the next reactor (Fig. 4). The analysis in
tor. As the product gas temperature at the combustor exit every single reactor control volume considers the solution
decreases with the increase in the excess supply of air, the of the governing equations for getting the concentrations of
maximum ability of it to perform useful work decreases. different species of interest and the temperature [40].
Therefore, the second-law efficiency decreases. The mass conservation equation of an arbitrary species i
The same decrease in exergetic efficiency is also observed may be written as
with the insufficient supply of air, when the exit tempera- dmcv
ture decreases because of the incomplete release of fuel’s k
¼m _ in
k m _ ex
k þm _ 000
k V, (17)
dt
stored energy. The maximum efficiency, which is obtained
with the stoichiometric supply of air, may be considered as where m _ 000
k is the rate of mass generation of the species k per
the ideal situation for every inlet air temperature. This ideal unit volume of the reactor and V is the reactor volume.
efficiency again increases with the increase in the inlet air Assuming steady-state operation of the reactor, the above
temperature which increases the temperature of the equation may be written as
 
product gas. m_ C in ex
_ k M k V ¼ 0,
k  Ck þ o (18)
Adebiyi [39] showed from a similar analysis in an
adiabatic combustor, assuming complete combustion with- where m _ is the total mass flow rate of the entire reactant or
out dissociation and constant specific heats of air and product streams and Ck is the mass fraction of the species
product gas, that the maximum second-law efficiency _ k is the chemical rate of formation of species k per unit
k. o
attainable for a combustion engine is 70% with CH4 as volume, expressed in kmol/m3 s, obtained from the kinetics
the fuel and keeping the product temperature within the of reaction. For the well-stirred reactor, the chemical
acceptable limit guided by the metallurgical constraint. reaction rate may be expressed as a function of the
temperature and the species concentration in the control
volume (i.e. at the outlet).
3.3.2. Analysis in well-stirred reactor
The steady state, steady flow conservation of energy
The above approach considering both infinite speed of
equation considering adiabatic reactor gives
transport and kinetics does not in any way involve the time !
scale for determining the performance of the process. An XN X
N

improvement may consider a well-stirred reactor model for m_ C ex


k hk ðT ex Þ  C in
k hk ðT in Þ ¼ 0, (19)
k¼1 k¼1
the combustor. A well-stirred reactor considers an infinite
rate of transport, while taking into account the speed of where the upper limit N of the index k denotes the number
reaction. In a practical reactor, high level of turbulence of species involved. The simultaneous solution of the above
ARTICLE IN PRESS
S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376 359

equations gives the species mass fraction and the tempera- the value of the second-law efficiency. However, this
ture at the exit of the reactor, when the inlet values are approach does not throw any light on the causes of the
known. Using the expressions for exergy (thermomechani- irreversibilities. In a combustor, several transport and
cal as well as chemical), as shown in the previous section, chemical processes take place simultaneously, which are
the exergy values at the inlet and exit of the reactor can be irreversible. The contribution of the processes towards
obtained from which the second-law efficiency can be entropy generation at different locations within the
calculated. combustor is required to be known to investigate the
This method includes in the calculation the volume of primary causes of exergy loss. It is also not practically
the reactor, as well as the chemical reaction rate for the possible to improve the performance of a combustor
species from the kinetic parameters. Therefore, the results without such information. The present approach fails to
from the method will be more realistic. provide this data and calls for a methodology, which
considers the irreversibility as a field variable to find its
distribution within the entire combustor.
3.3.3. Intrinsic analysis
As pointed out by Lior [34], the system level develop-
ment based on exergy calculation mostly use the equili- 3.4. Exergetic performance analysis using entropy
brium approach that employs equilibrium state data at the generation equation: approach 2
inlet and exit of the combustor for the exergy calculation.
However, such equilibrium may not prevail in reality The irreversibility present in the actual processes
within the actual combustor. The exact distribution of the occurring in a combustor results in the generation of
velocity, temperature and species concentrations in the entropy following the second law of thermodynamics. The
combustor can be numerically obtained from the detailed rate of entropy generation may be used to calculate the rate
solution of reacting flow inside the combustor. This of irreversibility or exergy destruction using the well-
requires the coupled solution of the full field and state known Gouy–Stodola equation (Eq. (2)). The determina-
equations consisting of the Navier–Stokes, energy, species tion of the total rate of entropy generation is an involved
conservation and thermodynamic property equations process in an intrinsic analysis in the combustor. This is
along with the equations of reaction kinetics. The field done by calculating separately the rate of entropy
parameters are then used in the transport equation of generation in each physical and chemical process that
exergy to find out the change in exergy flux between the takes place.
inlet and outlet amounting to the loss of exergy. The In the flow field of a combustor, the nonequilibrium
individual contribution of the kinetic, potential, thermal, conditions are due to the exchange of momentum, energy
strain and chemical exergy loss can also be obtained from and mass of different species (multicomponent) within the
the calculation. The expanded forms of individual compo- fluid and at the solid boundaries. These nonequilibrium
nents are given in Lior [34] and Lior et al. [35]. phenomena cause a continuous generation of entropy in
The calculation of exergy loss, as indicated in the the flow field. The entropy generation is due to the
referred papers, are complicated because of the complex- irreversible nature of heat transfer, mass diffusion, viscous
ities of the equations involved. However, the intrinsic effects within the fluid and at the solid boundaries,
analysis for the exergy loss calculation can be performed in chemical reaction, coupling effects between heat and mass
an alternative way [41]. The solution of the conservation of transfers and body force effects. Every irreversible process
mass, momentum, energy and species concentrations in the can be viewed as the relevant flux driven by the
combustor along with suitable kinetic rates of reaction corresponding potential, e.g. the flux of heat is driven by
generates information at the exit, typically for the velocity, the temperature gradient. The entropy production rates in
temperature and concentration of various species. The different processes can be explicitly obtained considering
exergy flow rate at the inlet to the combustor can be the conservation of multicomponent species mass in
obtained from the Eq. (10). While at the exit, the exergy presence of chemical reaction, conservation of momentum
flow rate is expressed as and energy along with the local entropy balance equation.
Z The local entropy generation per unit volume has been
X derived by Hirschefelder et al. [42] and is given by:
A_ ex ¼ C ex ex ex ex
k ak r uz dA, (20)
Areaex k
PK
tij ðqui =qxj Þ q_ i qT j k ðqwk =qxi Þ
000
s_g ¼  2  k¼1 i
where the exit variables are obtained as the output of the T T qxi T
numerical solution of the reacting flow. This method PK PK
s̄ j
k ki ðqT=qx i Þ j k fk
considers the local specific availability ‘a’ to bear the same  k¼1 þ k¼1 i i
T T
functional relationship with the pertinent thermodynamic PR PK  00 0

o_ c g  g w
kr k
properties as in case of equilibrium thermodynamics.  c¼1 k¼1 kr
, ð21Þ
The second-law efficiency obtained from the exergy T
approach gives a direct measurement of the performance of where tij is the stress tensor, q_ i is the heat flux vector and
the combustor. The larger the irreversibilities, lower will be j ki , wk and s̄k are the species mole flux per unit area,
ARTICLE IN PRESS
360 S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376

chemical potential and partial molal entropy of the kth cesses of momentum, heat and mass as well as includes
species, respectively. g0 kr and g00 kr are the stoichiometric chemical reaction. Therefore, for a sufficiently detailed
coefficients on the reactant side and product side, analysis, in addition to considering the contribution of
respectively, for the kth species in the cth reaction, and every process towards entropy generation, it is first
o_ c is the reaction rate of the cth chemical reaction. In the required to solve the combustion phenomenon itself,
above equation, the first term is due to fluid friction, the considering the maximum possible details. The accuracy
second due to heat transfer, the third due to mass transfer, in the simulation of combustion has a big role in correctly
the fourth is a result of the coupling between heat and mass predicting the exergy destruction.
transfer, the fifth term is due to the body force effects and Arpaci and Selamet [50] calculated the entropy genera-
the last term results from chemical reaction. tion in a premixed flame established on a flat flame burner.
Observation of the Eq. (21) shows that knowledge of the They developed an equation for local entropy production
field parameters like velocity (and hence tij), temperature considering the conservation equations of mass, momen-
(and hence qi), species concentration (and hence jk, mk), of tum and energy as well as the local entropy balance
the state equations of the species used to determine the equation as follows:
thermophysical properties (density, viscosity and thermal "   #
conductivity), and of the chemical reactions involved (to 000 1 k qT 2 qui 000
s_g ¼ þ tij þu . (22)
determine the rate) allow the computation of the entropy T T qxi qxj
generation fields and exergy destruction. All these field
parameters are obtained from the solution of the full field The terms in the bracket on the RHS show the contribu-
and state equations, consisting of the Navier–Stokes, tions of thermal diffusion, mechanical energy dissipation
energy, species conservation, entropy generation, and and the dissipation of other forms of energy towards
thermodynamic properties equations, combined in a entropy production (u000 ), respectively. In a flat flame
combustion process with the reaction kinetics equations, established on a burner, the authors considered one-
all tightly coupled. dimensional variation of temperature and obtained the
The rate of exergy destruction calculated from the local entropy production from the dimensional considera-
entropy generation rate in this approach, gives the local tion of the thermal part. They defined a non-dimensional
2
contribution of each individual process over the entire entropy production rate as Ps ¼ s_000 g l =k, where l is a
o
combustor. It therefore helps in identifying the process, characteristic length given as l ¼ a=ufl (a being the thermal
which has to be improved to reduce the loss. The above diffusivity and uofl the adiabatic laminar flame speed at the
equation, given by Hirschfelder et al. [42] has been later unburned gas temperature). It was shown from the analysis
used by other researchers for the calculation of entropy that the non-dimensional entropy generation rate is an
generation in non-reacting as well as reacting flows. Teng et inverse quadratic function of the flame Peclet number,
al. [43] further considered the contribution of the diffusive- given as PeoD ¼ uofl D=a, where D is the quench distance of
viscous effect towards entropy generation in a multi- the laminar flame, which was expressed as the distance of
component reacting fluid flow in addition to the other the flame from the burner [50]. Using the tangency
contributions as shown in Eq. (21). condition ðq=qyb ÞðPeoD Þ ¼ 0 during flame quenching (where
yb is the burned gas temperature normalized against the
4. State of art in exergy analysis in combustion adiabatic flame temperature), the authors showed that the
minimum quench distance corresponds to an extremum in
Both the approaches, described above have been used in the entropy production.
the literature for the analysis of exergy destruction in The distribution of rate of entropy production between
combustion. The calculation of exergy destruction in the flame and the burner was also shown in terms of the
consideration of the equilibrium states at inlet and outlet burned gas temperature and the distance from the burner.
is mainly used for the analysis of system design and does The entropy production rate between the flame and the
not help in identifying the root causes of exergy destruction burner appears to remain almost constant spatially, for
in the combustor. We shall exclude the review of such work yb oð1  yu Þ, where yu is the unburned gas temperature
and only consider those works, which give somewhat normalized against the adiabatic flame temperature. This
detailed information regarding the causes and locations of result was not surprising considering the small quench
irreversibility in different combustion situations. distance, which varies only between 0.5 and 1 mm. However,
Tracking entropy generation in a flowing fluid is used for when yb Xð1  yu Þ, an unusually rapid change in the
analyzing the energy conversion systems in many industrial distribution of entropy production was found from the
processes. Investigations of entropy generation in flows analysis. This result was indicated by the authors as a
have been reported in the literature related to momentum limitation of their model, which predicted a large deviation
transfer [7], heat transfer [7,8,10,11,44], mass transfer from the experimental results for this condition. The work
[45,46], combined heat and mass transfer [47,48] and of Arpaci and Selamat finds importance as it was probably
chemical reaction [49]. Analysis during combustion is the the first one, which applied the entropy generation approach
most challenging because it involves the transport pro- in combustion application. However, the simplistic physical
ARTICLE IN PRESS
S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376 361

situation and model adopted in the work failed to generate due to chemical oxidation reaction and 8–10% due to gas
detailed information from it. mixing. In the process path 2, 66–73% of the total exergy
In the literature of exergy analysis in combustion destruction was accounted to internal heat exchange,
systems, the work of Dunbar and Lior [6] receives a special 18–25% to chemical reaction and 8–10% to the mixing
mention, because they for the first time evaluated the processes. Therefore, Dunbar and Lior concluded no
primary causes for irreversibility using some heuristic finite perceptible difference in the causes of exergy destruction
increment exergy analysis method for the simple hydrogen due to the premixing of the reactants. Between hydrogen
and CH4 fuel combustors. The method adopted in the and CH4, a relatively higher percentage of irreversibility
work was not fully intrinsic as the authors did not solve the resulted due to chemical reaction in the latter case than that
full conservation equations with the reaction kinetics in the in the former. However, even with CH4 combustion the
combustion chamber to obtain the flux and gradient terms largest share of irreversibility resulted due to heat transfer
for the different processes involved. Instead they divided only. They also studied the effects of preheating using
the entire combustion phenomenon into a number of suitable choice of the process path.
hypothetical sub-processes and applied them along the The analysis of Dunbar and Lior was able to provide
prescribed process paths. The sub-processes considered by important information through a hypothetical approach.
the authors are: Subsequent to this, additional works have been reported in
the literature dealing with the detailed exergy analysis in
(i) a diffusion process where the fuel and oxygen various combustion phenomenon. In the following sub-
molecules are drawn together, sections these works have been briefly reviewed based on
(ii) a chemical reaction process leading to oxidation of the the type of fuel on which they have been applied.
fuel,
(iii) an internal thermal energy exchange between high- 4.1. Gaseous fuel combustion
temperature product and the unburned reactant,
(iv) a physical mixing process where the system constitu- Exergy analysis in gaseous jet flames have been studied
ents mix uniformly. by Datta [51,52], Stanciu et al. [53], Nishida et al. [54],
Datta and Leipertz [55] and Yapici et al. [56,57]. The
The sub-processes are arranged differently in the process studies include both non-premixed and premixed flames as
paths resulting in different types of combustion phenomena. well as laminar and turbulent jet flames. All these works
In one case (path 1), the authors considered an pertain to the numerical solution of the conservation
incremental quantity of fuel to be mixed with its equations to predict the combustion process and calcula-
corresponding stoichiometric quantity of oxygen to result tion of the volumetric entropy generation on a local basis
the chemical reaction, internal energy exchange and from the field values. The accuracy of the prediction is
product mixing (Fig. 5a). Such incremental process certainly a key factor in the determination of the exergy
continued along the length of the combustor in small loss, as the flux and gradient of the field variables
compartments till the gas constituents reached the fuel determine the entropy generation rate. The assumptions
ignition temperature after which the oxidation of the employed in the models, including those in the transport
remaining fuel was assumed to be instantaneous. The path and thermodynamic properties (e.g. unity Lewis number),
according to the authors corresponds to the behavior of a chemical reaction equation, etc. play important role to
diffusion flame. this effect. Following the approach given in Section 3.4,
In an alternative case (path 2), the entire fuel and air the Gouy–Stodola equation is used for the calculation of
were first mixed thoroughly (Fig. 5b). Subsequently, exergy loss. A complete field picture of the entropy
incremental amount of the mixture was reacted followed generation rate using Eq. (21) helps to identify the
by the internal energy exchange and mixing. Such a path key locations causing the exergy loss as well as the root
may exhibit the behavior of a premixed flame. cause of it.
Dunbar and Lior performed their analysis separately Datta [51] performed a numerical analysis of CH4–air
with hydrogen and hydrocarbon (CH4) fuels. It was found laminar non-premixed flame in a confined environment
that fixing the number of increments beyond an optimum (Fig. 6) and evaluated the volumetric rate of entropy
number does not change the results any further. Despite generation. A single-step chemical reaction and unity Lewis
the simplification, the analysis yielded consistent results. It number were the key assumptions in the model. The effect
was observed that, in each of the hypothetical paths, the of viscous dissipation was found to be negligible and
major share of exergy destruction took place due to the thermal diffusion, chemical reaction and mass diffusion
internal energy exchange. In the process path 1, the overall were found to contribute to the entropy generation in the
exergetic efficiency was reported to be within 66.5% and order of their enumeration. A study of parametric
77.3% in hydrogen combustion for a range of excess air of variation on the entropy generation rate was performed
0–100%, decreasing with the increasing amount of excess by varying the air inlet temperature, the thermal condition
air. Out of the total exergy destruction, 72–77% was at the confined wall (isothermal at 298 K, and adiabatic)
reported to be due to the internal heat exchange, 15–18% and the air–fuel supply ratio (by changing the fuel flow rate
ARTICLE IN PRESS
362 S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376

First Incremental Second Incremental


Extent of Reaction Extent of Reaction

Unreac.
Fuel Unreacted Fuel Fuel
Feed Fuel Incre.
Fuel Q
Incremental
Fuel H2O
Q H2O

H2O Product
H2O Stoich. Q
mixing
amount O2
Product
Q mixing
Stoich.
amount O2
Air Rest
Product
Feed Rest amount
amount

First Incremental Second Incremental


Extent of Reaction Extent of Reaction

Fuel
Feed

Thermal Incremental Thermal


Fuel-Air Incremental
Energy Reaction Energy
Mixing Reaction
Exchange Exchange

Air
Feed

Fig. 5. (a) Hypothetical combustion chamber for process path 1 with H2 as fuel [6]. (b) Hypothetical combustion chamber for process path 2 [6].

while keeping the airflow constant) in gauging the relative Nishida et al. [54] studied a typical unconfined laminar
role of chemical reaction, internal heat and mass transfer in non-premixed flame for the analysis of the local entropy
entropy production within the combustor only. However, generation. The conservation equation of entropy was
the entropy production in combustor together with that in solved with a source term containing contributions of
air pre-heater determines the energy economy of the viscous dissipation, heat conduction, mass diffusion and
combustion system comprising both the combustor and chemical reaction. The radial distribution of species mole
air pre-heater. It can be mentioned in this context that an fraction and temperature at a single axial height as also the
exergy analysis of an air pre-heater requires information local entropy generation rate for each irreversible process
about the thermodynamic states of air and hot gas at entry at the same height were presented. The contribution of
and exit to the heater which in turn depend upon its thermal conduction was seen to far outweigh the contribu-
physical location in the plant. tion of chemical reaction towards entropy generation. The
Stanciu et al. [53] showed that in a constant pressure authors reasoned that the high temperature in the zone of
laminar non-premixed flame the irreversibilities due to chemical reaction in a non-premixed flame is the cause of
viscous dissipation, heat conduction, mass diffusion and its lower contribution to entropy generation.
chemical reaction are uncoupled. The authors also showed Though the work of Nishida et al. [54] gave the radial
that in a CH4–air combustion process, the thermal, distribution of entropy generation rate at a single axial
chemical and diffusive irreversibilities represent, in order location, a complete representation of the irreversible
of enumeration, the predominant irreversibilities in the processes over the entire field is absent in it. Such a
laminar diffusion reacting flows. complete irreversible field could be envisaged in a later
ARTICLE IN PRESS
S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376 363

dout

di

Fig. 7. Temperature distribution in a laminar methane–air jet diffusion


flame with the flame contour shown in black line [52].

temperature zone is located within the flame in an annular


Air Fuel Air region somewhat above the burner port. The high
temperature causes a buoyant acceleration to the flow in
din
the flame zone and thereby entrains air from the
d surrounding resulting in a flow field that generates
the over-ventilated structure of the flame. Moreover, due
to the continued entrainment towards the core, the
Fig. 6. Schematic of the co-flow confined burner used for the computation pressure near the periphery drops resulting in an ingress
of thermodynamic irreversibilities in jet diffusion flame [51,52]. of air from the atmosphere through the exit plane. The
ingress causes the formation of a recirculation over the
outer wall and results in a low temperature shield over
work of Datta [52], which studied the role of gravity on the the wall. The complete picture of flow may be available in
entropy generation in a laminar non-premixed CH4–air the original work [52]. At the core, the temperature
flame in the same configuration as in Fig. 6. The numerical gradually reduced downstream to the flame zone due to
model employed a two-step chemical reaction and the the transport of heat due to internal heat exchange.
variation in the property values based on local temperature Figs. 8a–e show the concentration distributions of
and species concentration. The kinetic parameters were the major species like fuel (CH4) and O2, which are the
adjusted to give a reasonably correct prediction in the field reactants, and CO, CO2 and H2O, which are the
variables, which was ascertained by comparing the intermediate and final products. The distributions are
distribution of the field variables against the experiment. the result of the transport process of the species mass in a
It was assumed that the low flux of the intermediate species multicomponent environment as well as chemical reaction.
because of their low concentration, would not contribute The fuel coming from the central jet is consumed at the
much towards entropy generation and the major species, flame and its concentration gets rapidly reduced. There-
whose concentrations were predicted in the model, were fore, the fuel species exist only inside the flame region. The
solely responsible to the entropy production process. oxygen supplied from air enters as the co-flow and
Fig. 7 typically illustrates the structure of a laminar non- transports towards the flame from the peripheral side. It
premixed flame predicted by the numerical model [52]. The gets consumed at the flame surface and therefore within the
figure plots the temperature distribution in the confined flame region only a trace of it is located. CO is found inside
domain near the core, where the flame exists. The plot near the flame. It is formed on the inside surface of the flame,
the wall is not shown as there is almost no variation of which burns in a rich atmosphere because of the shortfall
temperature there. The flame contour is also plotted in the of oxygen. The CO that comes towards the outer surface of
figure by drawing the heat release zone. The highest the flame front gets readily consumed with oxygen. On the
ARTICLE IN PRESS
364 S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376

Fig. 8. Distribution of concentration of different species in methane–air jet diffusion flame: (a) CH4, (b) O2, (c) CO, (d) CO2 and (e) H2O.

contrary, absence of oxygen inside the flame allows CO to sudden reduction in concentrations of the reactants and
diffuse inside showing its existence inside the flame. CO2 generation of products result in large rates of transport of
and H2O are formed in the flame front and are transported the species. The transport processes of heat and mass as a
in all directions based on the advective and diffusive rates. result of the temperature and concentration distributions
The transport of the product species continues downstream occur through irreversible processes and result in entropy
to the flame till the exit plane is reached. However, the generation. The entropy generation rate is high at locations
major mass transport occurs in the flame region, where the where the field gradient and the resulting fluxes are high.
ARTICLE IN PRESS
S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376 365

Fig. 9. Rate of volumetric entropy generation in methane–air laminar jet diffusion flame due to (a) chemical reaction, (b) heat transfer, (c) mass transfer.

Figs. 9a–c illustrate the plots of the local volumetric diffusion is less than that due to chemical reaction.
entropy generation rate contours due to chemical reaction, However, the entropy generation due to heat diffusion
heat transfer (thermal diffusion) and mass transfer occurs over a much greater volume compared to the
respectively, for the non-premixed flame. It is evident from volume of the flame, where entropy is generated due to
the figure that the entropy generation due to chemical chemical reaction. In the flame zone, heat diffusion occurs
reaction (Fig. 9a) takes place within the flame front. The from the high-temperature flame. Moreover, the buoyancy-
volumetric entropy generation rate due to chemical induced acceleration increases the flow velocity at the core
reaction is higher near the base of the flame. It reveals and results in a high entrainment of fluid towards the
that the flame is more intense near its base. At the tip, the center. The flow structure generates a thermal stratification
flame is weak and the volumetric entropy generation rate is with the high-temperature gas near the core. Due to the
less than 1/20th of the peak contour value shown in the axi-symmetric nature of the flow the gradient of tempera-
figure. The concentration gradient of the fuel is more at ture remains low near the axis. The ingress of atmospheric
lower elevation and results in higher rate of diffusion of air through the outlet plane and formation of the
fuel towards the flame front. This makes the flame more recirculation zone around the peripheral wall maintains a
intense there. With the consumption of fuel, the fuel low temperature shield at the periphery. There exists an
concentration gradient reduces at higher elevation. This annular region between the core and the wall, where the
decreases the fuel transfer rate to the flame and the flame temperature falls rapidly causing a high rate of heat
intensity also decreases. An inner reaction zone is also transfer. The stratification of the flow and the formation of
evident from the chemical entropy generation plot, which the recirculating zone due to atmospheric air ingress
however is much weaker. In a jet diffusion flame, the flame maintain the annular region of high-temperature gradient
is little lifted from the burner depending upon the jet till the exit plane. Therefore, high diffusion of heat
momentum. Through the gap some air diffuses in to form a continues over a much larger volume to cause a high
weak premixed flame in the core. Therefore, the entropy overall entropy generation rate.
generation field portrays a good picture of the flame The entropy generation due to mass transfer of all the
structure. species is depicted in the Fig. 9c. It is observed that the
Fig. 9b shows the volumetric entropy generation rate due mass transfer results in entropy generation mainly around
to thermal diffusion in the confined domain. The strong the flame. In a diffusion flame the reactants diffuse into
temperature gradient close to the burner rim, where the the flame from the opposite sides of the flame surface and
flame is stabilized, increases the entropy generation there. the products transport from the flame in all directions.
The peak volumetric entropy generation rate due to heat Beyond the flame, though transport of heat continues,
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366 S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376

mass diffusion ceases to play any major role. The figure


reveals that the magnitude of the rate of entropy
generation per unit volume due to mass transfer is
significantly lower compared to the other two major
contributors even in the flame zone. Though generation
and consumption of different species occur in the flame, the
gradient of species concentrations never takes a large value
and the transport process always bring a uniformity in the
distribution of the species around the flame. The only high
rate of entropy generation due to mass transfer is observed
just above the entry plane and around the interface
between the fuel and air jets.
The field values of the rate of entropy generation give a
complete picture of the causes of irreversibilities and their
location in the flame. It was observed that the gravity has a Fig. 10. Variation of the rate of entropy generation (total as well as for
major role in controlling the entropy generation rate in the individual processes) and exergetic efficiency in a confined laminar
flame. In a reduced gravity environment, the flame and diffusion flame at different gravity levels [52].
flow characteristics experience a major change. At zero
gravity, the buoyancy-induced flow is totally absent
reducing the entrainment of air from the surrounding Table 1a
towards the flame. The flame therefore becomes less intense Inlet operating parameters for different numerical experiments in non-
and the volume of the flame increases as it achieves a premixed gaseous jet flames [51]
somewhat spherical shape instead of the elongated over- Sl. no. Inlet section
ventilated shape at normal gravity. The volumetric entropy
generation rate due to chemical reaction shows a reduction 0orpR1 R1orpR2
in its peak value at zero gravity than at normal gravity due Fuel jet Fuel jet Air jet velocity Air jet temp.
to reduced intensity of the flame. However, the total rate of velocity (cm/s) temp. (K) (cm/s) (K)
entropy generation due to chemical reaction is not much
different because the volume of the flame front at zero 1 4.5 298 9.88 298
2 4.5 298 14.55 450
gravity level is more due to the increased width of the 3 4.5 298 19.89 600
flame. The higher volume of the flame front compensates 4 6.0 298 9.88 298
the decrease in the volumetric entropy generation rate that 5 7.5 298 9.88 298
takes place at zero gravity. On the other hand, the entropy
Diameter of the central fuel port (R1) ¼ 12.7 mm.
generation rate due to heat transfer is reduced considerably Diameter of the annular co-flow tube (R2) ¼ 50.8 mm.
at zero gravity compared to that at normal gravity. This is Pressure ¼ 1 atm.
because in a zero gravity non-premixed flame the reduced Wall condition: adiabatic.
entrainment from the co-flow results in a more uniform
radial temperature distribution. The entropy generation gravity level, the entropy generation due to reaction and
due to mass transport, which is in effect low, is not much mass transfer hardly changes in magnitude. However, the
different at reduced gravity from the corresponding value entropy generation due to heat transfer is grossly affected
at normal gravity. by gravity. It is already explained that as the gravity level is
Fig. 10 shows a plot of the total rate of entropy reduced the temperature field becomes more uniform and
generation in the confined domain and the rate of entropy the entropy generation due to heat transfer decreases. This
generation due to individual processes in non-premixed decrease in the entropy generation is also reflected in the
flame at various gravity levels varying from normal gravity total entropy generation rate and results in a decrease in
to zero gravity [52]. The corresponding Froude number the total entropy generation.
(Fr ¼ gd i =u2f , where g is the acceleration due to gravity, di Tables 1a and 1b show the details of the operating
the fuel port diameter in the burner and uf the fuel jet conditions studied and the entropy generation values
velocity at burner exit) varies in the range of zero (at zero obtained in the non-premixed laminar gaseous jet flame
gravity) to 61.33 (at normal gravity). The entropy in a confined environment [51]. The effect of preheated air
generation due to fluid friction is not included in the figure on entropy generation showed that the total rate of entropy
due to its very low value. It is seen that out of all the generation decreases with the increase in inlet air tempera-
individual processes, the most dominant role towards ture. The variation is principally attributed to the decrease
entropy generation in non-premixed flame is played by in the contributions of the thermal diffusion and chemical
heat conduction under all gravity conditions. Chemical reaction. The higher value of air temperature increases the
reaction is the next significant contributor and mass flame temperature but decreases the temperature gradient
transfer comes as the third important. With the change in occurring in most of the region of the domain resulting in
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S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376 367

Table 1b
Rate of entropy generation (W/K) at different inlet conditions given in Table 1a

Sl. Inlet air Air–fuel Entropy generation rate due to transport Entropy gen. rate Total rate of
no. temp. ratio in chem. reaction entropy
Heat Mass Combined heat- Total in generation
transport transport mass transport transport

1 298 59.29 0.3650 0.0440 0.1004 0.5094 0.1429 0.6523


2 450 59.29 0.3120 0.0464 0.0796 0.4380 0.1376 0.5757
3 600 59.29 0.3017 0.0489 0.0670 0.4177 0.1341 0.5519
4 298 44.46 0.3999 0.0503 0.1158 0.5661 0.1675 0.7337
5 298 35.57 0.4356 0.0670 0.1294 0.6224 0.1935 0.8159

a reduction in the diffusive heat flux. These together are the entropy generation from the entropy balance equation
primary cause of the lower contribution of thermal given by the second law of thermodynamics.
diffusion towards entropy generation. The chemical reac- The highest exergy exists in the fuel, which represents the
tion occurring in the high-temperature flame reduces its maximum potential of the fuel to perform work. When this
contribution to the entropy generation rate. chemical energy is transformed into thermal energy, some
The effect of increase in the fuel flow rate was found to portion (which depends on the final temperature) of the
increase the total entropy generation rate in the domain. initial availability is destroyed. The amount of the exergy
The contribution of both the transport processes and that is destroyed increases for lower final temperatures of
chemical reaction was found to increase. The height of the the product, i.e. for lower flame temperature. The higher
non-premixed flame increases with the increase in the fuel initial temperature of the reactant decreases the destruction
flow rate. The increased volume of the flame is the primary in exergy in the combustion process due to the higher
cause of the increased rate of entropy generation. temperature of the product, which retains more exergy
The other class of gaseous fuel combustion is the contained in it. Regarding the effect of the equivalence
premixed flame, where the fuel is considered to be ratio, the author found that the destruction of exergy per
homogeneously mixed with the oxidizer before reaching unit mass of the fuel increased as the reactant mixture
the reaction front. Caton [23] performed a somewhat became leaner than stoichiometric. This may be attributed
simplified analysis in an adiabatic, constant volume to the lower temperature of the flame in a lean mixture and
chamber, where the exergy loss in a combustion process the inherent irreversibility associated with the mixing of the
is analyzed based on thermodynamic calculations con- combustion products with the excess air present in the
sidering equilibrium. Though the fuel considered was combustor. As a recommendation from the study, Caton
octane, the author assumed a pre-vaporized mixture of it observed that in an internal combustion engine the reactant
with air. The features of liquid fuel combustion, like temperature should be kept high to ensure less exergy
evaporation and mixing of the fuel vapor and air were not destruction. However, the author also reminded that the
considered. We have therefore included the work here as realization of the exergy depends on the application
gaseous fuel combustion. following the combustor. For example, he suggested that
As there was neither heat and work transfer across the to recover the maximum work from the high exergy
system boundary nor any additional mass exchange during content of exhaust gases, exhaust devices like turbo-
the process, the author claimed the difference of exergy compounding have to be employed in the engine. The
before and after the chemical reaction was solely due to author also pointed out that the high initial temperature
combustion. A homogeneous mixture of species in the for recovering maximum exergy in combustion may result
combustor was assumed giving spatially uniform proper- in other issues like increased NO emission.
ties. The combustion reaction was assumed to be complete Nishida et al. [54] performed a detailed numerical
and the product concentrations were calculated from analysis for the study of exergy loss in a laminar premixed
chemical equilibrium consideration at high temperature. flame. The conservation equations of mass, momentum,
The first and second laws of thermodynamics were used to energy and species were solved taking into account the
calculate the properties before and after the reaction. The detailed chemical kinetics and multi-component diffusion.
exergy quantities before and after the reaction were The thermodynamic and transport properties were ob-
calculated considering the thermomechanical contribution tained from the CHEMKIN database. Premixed flames
of all the species and the additional chemical exergy were simulated using the steady, one-dimensional flow at
contribution of the fuel species. The chemical exergy of the atmospheric pressure and with hydrogen and CH4 as the
fuel was obtained from the difference between the Gibb’s fuels. The entropy generation rate was calculated using the
free energy of the product and reactant at the reference field variables and considering the contributions of viscous
state. The exergy destruction was further checked intern- dissipation, heat diffusion, mass diffusion and chemical
ally against the process irreversibility calculated using the reaction. It has been shown that the total rate of entropy
ARTICLE IN PRESS
368 S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376

generation becomes large in the region of the main reaction entropy generation decreased and the exergy destruction as
zone denoted by the high-temperature gradient. Chemical a fraction of fuel’s exergy was reduced. However, the
reaction accounted for the maximum entropy generation contribution of chemical reaction towards the total entropy
both in hydrogen and CH4 flames, while heat conduction generation increased.
contributed the second largest. While in a stoichiometric A contrasting feature of the predictions of Nishida et al.
hydrogen–air flame with 25 1C reactant temperature, [54] and those of Dunbar and Lior [6] in premixed flame is
72.6% of the total entropy generation rate was contributed that while the former found the chemical reaction as the
by chemical reaction, in a stoichiometric CH4–air flame the most significant contributor the latter attributed the same
percentage contribution of chemical reaction was 55.3%. to heat diffusion. Though Dunbar and Lior performed a
The contribution of heat conduction for the two cases were hypothetical analysis, they considered chemical reaction in
found to be 21.6% and 37.9%, respectively. The effect of incremental quantities followed by internal heat exchange
mass diffusion was found to be much smaller and the effect in the mixture. On the other hand, Nishida et al. considered
of viscous dissipation is negligible. a one-dimensional analysis typical for a flat flame situation.
From the spatial distribution of the entropy generation In a flat flame, the temperature varies from the reactant
rate shown by the authors, it is evident that in the hydrogen temperature to the product temperature within a small
flame the steep rise in the entropy generation rate due to thickness of about 0.5–1 mm, outside which the tempera-
chemical reaction and heat conduction initiates at the same ture gradient is reasonably flat. Therefore, the entropy
axial location, though the peak for the chemical reaction generation due to heat diffusion is only effective within a
occurs at a little downstream location. However, the short volume and the effect of irreversibility remains low.
temperature where the entropy generation due to chemical Most of the reacting flows occurring in the engineering
reaction reaches the peak was found to be sufficiently low. devices are turbulent. In this case, the fluctuating field is
In the CH4 flame, however, the entropy generation due to maintained by the turbulent production terms. At the
chemical reaction increased much later compared to the larger scales of turbulence, they extract a part of energy (or
entropy generation due to heat conduction. Therefore, the exergy) from the mean flow field and through the vortex
peak in the entropy generation due to chemical reaction stretching mechanism continuously transfer it to the
shifted to a much downstream location compared to the smallest turbulent scales, where the molecular diffusivities
peak due to heat conduction. The temperature at the of multicomponent fluid perform its dissipation. Following
location where the entropy generation rate due to chemical this idea, Stanciu et al. [53] split the turbulent reacting flow
reaction peaked was much higher in CH4 flame than in irreversibility not only into the viscous, thermal and
hydrogen flame. This was attributed to the increased diffusion components but also into its mean and turbulent
concentration of the radical species in the flame. According parts. They used the phenomenological multi-species
to the authors, the high temperature in the flame region of approach and proved that 98% of the exergy destruction
CH4 combustion reduced the entropy generation rate due resulted due to the last part.
to chemical reaction and its contribution towards total Yapici et al. [56,57] studied the entropy generation in a
entropy generation was less than that in hydrogen flame. It turbulent swirl flow axisymmetric combustor with CH4 as
indicated the importance of the flame chemistry in the fuel. The fuel and air streams entered the combustor as
determining the exergy destruction in combustion. coflow, with swirl imparted to the airflow using inlet
In a study of parametric variation [54], the authors swirler. The former work [56] studied the effects of
found that the total destruction of fuel’s exergy increased equivalence ratio and swirl ratio on the entropy generation
when the premixed mixture was leaner than stoichiometric, rate, while the latter work [57] studied the influence of fuel
while an increase in the reactant temperature was found to type. The turbulent quantities were evaluated using the
decrease the percentage of total exergy destruction. In a RNG-k–e model, while the eddy dissipation model was
lean mixture, the temperature in the reaction zone was used for the calculation of the reaction rates. The CH4–air
found to rise more gradually resulting in a wider reaction reaction was assumed to proceed in two steps, with the
zone than that in stoichiometric mixture. Consequently, the intermediate formation of CO. The entropy generation rate
entropy generation zone of each process in the flame was considered to contain terms related to viscous
became wider. Though the fraction of entropy generation dissipation and heat conduction only. Such consideration
due to each individual irreversible process was similar to is applicable in heat transfer problem but fails to give the
that in a stoichiometric flame, the wider flame zone resulted complete picture of exergy destruction in combustion since
in the increase in total rate of entropy generation increasing the irreversibilities associated with mass transfer and
the exergy loss. With an increase in reactant temperature, chemical reaction are not considered. It remains the major
the flame temperature was increased correspondingly. The drawback in the works.
flame became narrower reducing the prime zone of entropy The numerical solution of combustion gave a tempera-
generation. The entropy generation due to heat conduction ture field with very high-temperature gradient. Swirl in the
became smaller as the inlet and outlet fluid temperature flow was found to affect the temperature gradient at low
rose. The high-temperature flame reduced the entropy value of fuel jet velocity, while at high fuel jet velocity this
generation due to chemical reaction also. Thus, the total effect was minimal. In all the cases studied, the entropy
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S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376 369

generation due to heat transfer was found to dominate over decreased exponentially with the increase in equivalence
that due to viscous dissipation. The highest local entropy ratio for the conditions of fuel flow rate studied. However,
generation rate was observed at the entry plane and near at a particular equivalence ratio, the total entropy
the wall. generation in the combustor increased with the increase
Parametrically the swirl number, equivalence ratio and in the fuel flow rate and therefore the heat transfer rate.
the fuel flow rate were all found to be affecting the entropy The incremental increase in the entropy generation for the
generation rate in the combustor [56]. The authors same incremental increase in the heat transfer rate was
proclaimed that, at no swirl, the entropy generation rate more at lower values of equivalence ratio. For the various
decreased exponentially with the increase of equivalence hydrocarbons studied, it was observed that the entropy
ratio (in the lean side between 0.5 and 1.0) for high fuel generation excepting with C2H4 and C2H2 were very close
injection rate, whereas they had quadratic profiles with to each other. Merit number was found to increase by
minima in the case of low fuel flow rate. However, it about 16% for the increase in the equivalence ratio from
appeared from their results that the variation is similar for 0.5 to 1.0.
all the fuel flow rates. Only difference being that at high
fuel flow rates the said minima did not come in the range of
4.2. Liquid fuel combustion
equivalence ratio of 0.5–1. At a constant fuel flow rate of
10 lpm, the entropy generation rate was found to decrease
4.2.1. Droplet exergy models
with the increase of swirl number.
The work of Dash et al. [58] is probably the pioneering
The variation in the entropy generation rate should
work in ascertaining the sources of irreversibility in course of
depend on the peak temperature reached in the flame and
evaporation of a single component liquid fuel droplet in a
the structure of the flame in the combustor. In a
high-temperature convective gaseous medium. The thermo-
stoichiometric flame, the peak temperature is higher than
dynamic irreversibilities were characterized by the rate of
a lean flame while, in a lean flame due to the higher flow
entropy production in the transport processes and were
rate of air, the flame can not spread radially, giving a high
determined from the field values of volumetric entropy
gradient of temperature and a high rate of entropy
generation rate as described in approach in Section 3.4.
generation. It shows that the flame structure has a strong
A break-up of entropy generation rate due to different modes
effect on the entropy generation rate due to heat transfer.
of transport processes in gas and liquid (droplet) phases
The merit factor, which is the ratio of the useful exergy
depicted that the entropy generation rate due to viscous
transfer rate through the wall and to the fluid to the sum of
dissipation was negligibly small because of low flow velocities.
the exergy transfer rate and the rate of irreversibility, was
Irreversibilities in droplet phase were also found to be quite
also calculated in the work. It was shown that for high fuel
insignificant compared to those in the gas phase. The most
flow rate, the merit factor continually increased with the
significant contribution in the total entropy generation rate
increase in equivalence ratio, showing the reduced influence
was due to the conduction of heat and its coupled effect with
of the irreversibility. While, for low mass flow rate, the
mass transfer in the gas phase. The rate of entropy
merit factor reached a maximum at a particular equiva-
production decreased continuously at a rate lower than the
lence ratio and then sharply decreased with a further
decreasing rate of droplet surface area. A numerical
increase in the equivalence ratio. A marginal increase in the
correlation of entropy generation rate with pertinent
merit factor was observed with the increase in swirl at a
dimensionless input parameters was developed as [58]
fixed fuel flow rate and equivalence ratio.
0  1:02 1:29
The second study [57] calculated the entropy generation S_ g M 1 =M v B
rate with a large number of fuels, e.g. hydrogen, CH4, 0 2
¼ 714:5 0:72
, (23)
r 0:66
ðRePr Þ
C2H2, C2H4, C2H6, C3H8, C4H10, C6H6 burning in air. For
0  
the sake of comparison, the fuel flow rates were adjusted to where S_ g ¼ S_ g r1 Rur2i is the dimensionless entropy
give the same heat transfer rate in the combustion generation rate, r is the density, R is the gas constant, u is
chamber. In all the studies it was found that the maximum the flow velocity, r0 is the dimensionless droplet radius ( ¼ r/ri),
reaction rates decreased with the increase in the equiva- Re is the Reynolds number of flow past the droplet, Pr is
lence ratio in the lean side of mixture stoichiometry. The the Prandtl number of gas flowing around the droplet, and
increase in the equivalence ratio also reduced the tempera- B is the transfer number. The subscripts N and i refer to
ture gradients in the combustor. Therefore, the volumetric the free-stream condition and initial state of the droplet,
local entropy generation rate was found to decrease with respectively. MN and Mv are, respectively the molecular
the increase in equivalence ratio from 0.5 to 1. Bejan weights of free-stream gas and droplet liquid. The relation-
number (ratio of entropy generation due to heat conduc- ship given by Eq (23) provides the fundamental informa-
tion to that due to both heat conduction and viscous tion in exergy-modeling of spray combustion, in a similar
dissipation) remained high (around 0.995) for all the cases fashion, Nusselt number relation of single droplet does in
indicating the negligible influence of viscous dissipation heat transfer modeling of spray combustion.
towards entropy generation, compared to heat conduction. The identification of irreversibility components and
The overall rate of entropy generation for any fuel subsequent exergy analysis in droplet combustion require
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the determination of entropy generation in a chemically 10


Dai = 12.22 x 106
reacting flow. The pertinent information in this regard has Curve T I
been reported by Hiwase et al. [59], Dash and Som [60], I 3.0
II 4.0
and Puri [61]. It was observed [59] that in spherico-
symmetric droplet combustion, the entropy generation rate 1
II
due to chemical reaction was of the same order as those due
to heat conduction and combined heat and mass convec-
tion. However, the entropy generation rate due to heat

Ichem / I-Ichem
0.1
conduction in gas phase was still the dominant factor,
though the entropy generation rate due to chemical
reaction shot up to a higher value at the instant of ignition.
The interesting outcome of this fact is that, in a typical
0.01
diffusion-controlled droplet combustion process, the irre-
versibility rate due to chemical reaction is lower than that
due to diffusion processes taken together, except at the
instant of ignition. This is shown in Fig. 11. In a convective 0.001
ambience, the total entropy generation rate (or irreversi- 0.1 1 10 100
bility) per unit droplet surface area increases as the burning t
of droplet progresses and reaches its highest value at the
Fig. 11. Temporal histories of the ratio of irreversibility due to chemical
end of droplet life when the droplet surface area becomes reaction alone to that of the diffusion processes taken together in a droplet
extremely small [60]. combustion [59].
A typical variation in second-law efficiency, for the
process of a n-hexane droplet combustion in a quiescent
ambient of air, with initial Damkohler number (Dai) at 1
various free-stream temperatures is shown in Fig. 12. The
parameter Dai physically signifies the ratio of characteristic
0.8
thermal diffusion time to chemical-reaction time. II I
A variation in Dai for any given fuel, under fixed values III
of initial gas-phase properties, implies a variation in the 0.6
II

initial diameter of the droplet. The upper flat portions of Curve T∞


the curves (Fig. 12) correspond to the process of pure 0.4 I 2.0
droplet vaporization without combustion in the gas phase, II 3.0
III 4.0
while the lower flat portions pertain to the steady-state
0.2
droplet combustion process. It is observed from the figure 0.01 0.1 1 10 100
that a low value of Dai and a high value of free-stream Dai × 10-6
temperature for the process of droplet combustion are
needed from the view point of energy economy in relation Fig. 12. The exergetic efficiency of a droplet combustion process [59].
to efficient utilization of energy resources. In a convective
ambience, the minimum entropy generation for the burning
of a fuel droplet corresponds to an optimum transfer In the expression, Ur is the relative velocity between the
number, which is directly proportional to the square of the droplet and ambient. hfg is the latent heat of evaporation
relative velocity and inversely proportional to the heat and Q is the heat release from the fuel droplet. TN and Tf
release rate and the temperature difference between the are the free-stream temperature and fuel droplet tempera-
droplet and its surrounding flow [61]. For flow with small ture, respectively.
Reynolds number, the expression for optimum transfer In a real system there is a little control over the transfer
number can be written after Puri [61] as number and the heat release. The specific enthalpy
 5 associated with the products is fixed by the choice of
O liquid fuel and the stoichiometry related to the oxidizer
BM;opt ¼  1, (24)
2 content in the gas. Under the circumstances, Eq. (24)
describes an optimum relative velocity that minimizes
where
the entropy generation or exergy loss for a given gas
3 U 2r flow rate and temperature ratio (ratio of free-stream
O¼    temperature to flame temperature). It should be mentioned
5 Q þ hf T1
hfg 1 1 in this context that the irreversibility analysis of droplet
hfg Tf
  evaporation and combustion as discussed above pertains to
1 T1 the laminar flow of the gas phase past the liquid fuel
 w ; wp;f . ð25Þ
M f p;1 Tf droplet.
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4.2.2. Spray exergy models 0.850


The identification of irreversibility components from Rei = 60 n=3
entropy generation rate in a spray combustion process is 0.825
composed of two parts, namely: (i) the entropy generation
in the evaporation of individual droplets in their local 0.800
surroundings due to interphase transport processes and
(ii) the entropy generation due to transport processes and

II
0.775
chemical reaction in the continuous carrier phase. A break-
up of the source of irreversibilities in a spray combustion
0.750
process shows equal order of magnitudes for the irreversi- Rei = 30
bility contributed by local interphase transport processes
0.725
and that contributed by the transport processes and chemical
reactions in continuous gas phase. The exergy balance and
0.700
the second-law analysis of a spray evaporation process in a
1.50 1.75 2.00 2.25 2.50 2.75 3.00
gaseous surrounding with uniform free stream were reported T∞
by Som et al. [62] and Som and Dash [63]. The entropy
generation rate in the evaporation of a liquid spray is initially Fig. 13. Exergetic efficiency of a spray evaporation process with
very large and then decreases with the axial distance of the Rosin–Rammler function as initial drop size distribution [63].
vaporizing spray. The rate of entropy generation increases
with an increase in the ratio of free stream to initial droplet The recent investigations of Datta and Som [64], Datta
temperature or with a decrease in the initial Reynolds [65] and Som and Sharma [66] provide comprehensive
number of the spray based on initial droplet velocity and information on energy and exergy balance in a spray
Sauter mean diameter of the initial PDF of the spray. combustion process in a gas-turbine combustor. The
The variation in second-law efficiency of a spray analyses employed a spray combustion model based on
evaporation process with governing parameters, as predicted stochastic separated flow (SSF) approach. The gas-phase
by Som et al. [62] and Som and Dash [63] depicts conservation equations were solved in an Eulerian frame,
different kinds of picture. The second-law efficiency ZII, while the droplet phase equations were computed in a
evaluated using ‘‘discrete droplet model’’, shows an initial Lagrangian frame. The interphase source terms were
increase in ZII with the free-stream temperature TN followed evaluated during the droplet phase computation and
by an almost constant value thereafter. This implies introduced in the gas phase. The turbulent quantities were
physically an optimum value of TN above, which the modeled using a standard k–e model and the chemical
evaporation of spray is not thermodynamically justified, reaction employed the eddy dissipation model. It was
since the increase in the rates of exergy transfer and that in found that the inlet air pressure had a marked influence in
its destruction become almost equal. However, the picture is decreasing the irreversibility due to interphase transport
different when the ‘‘two-phase- separated-flow model’’ is processes (Id), while the irreversibility in the continuous
used [63] to evaluate the second-law efficiency (ZII). Under gas-phase (Ig) was almost uninfluenced by the air pressure.
this situation, ZII shows a monotonically decreasing function At high air pressure, the value of Id is relatively lower than
of free-stream temperature and an increasing trend with the value of Ig, while the picture was reversed at lower
initial Reynolds number of the spray (Fig. 13). The pressure of ambient air. This can be attributed to a
qualitative difference in the results of [62] and [63] can be reduction in droplet vaporization rate because of a
attributed to the fact that in the ‘‘discrete droplet model’’ reduction in mole fraction of fuel vapor at droplet surface
adopted by Som et al. [62] for spray calculation, the with an increase in local pressure at a given local
transport processes in the carrier phase was neglected as it temperature. An increase in inlet air temperature increases
was considered to be a homogeneous gas phase with free- the irreversibility in the interphase transport process, while
stream properties. On the other hand, the separated-flow the gas phase irreversibility remains almost the same.
model for spray calculation [63] considered all the transport The exergetic efficiency in a typical spray combustion
processes in the carrier phase along with the interphase process lies between 50% and 70%, while the combustion
transport processes between the gas phase and the efficiency in case of gas turbine combustion lies between
evaporating droplet phase. Therefore, the earlier work [62] 90% and 98% under usual operating conditions.
underestimated the total entropy generation in spray A comparative picture of exergetic efficiency and combus-
evaporation process due to the lack of additional contribu- tion efficiency in spray combustion in a typical gas turbine
tion towards entropy generation due to the gas-phase combustion process at different operating conditions is
processes. The optimum values of free-stream temperature shown in Table 2 [64]. The interesting feature observed, in
and spray Reynolds number should be chosen as suggested this context, is that the qualitative trends of the influence of
by Som and Dash [63] on the basis of an overall economy inlet swirl number of incoming air on both second-law
which is a trade-off between the length of evaporation and efficiency and combustion efficiency are exactly the
total irreversibility of the process. opposite when the combustor pressure is changed from
ARTICLE IN PRESS
372 S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376

a lower to a higher value. While, at a low pressure of Table 2


100 kPa, an increase in inlet swirl increases the second-law Comparison of combustion efficiency (%) and exergetic efficiency (%) in
spray combustion [64]
efficiency (ZII) and reduces the combustion efficiency, (Zc),
the trends are reversed when the combustor pressure is (a) Influence of inlet pressure
increased to a value of 600 kPa. At low pressure, the
adverse effect of reduced droplet penetration due to an _ in
Inlet conditions: m a ¼ 0:1 kg=s, Rein ¼ 52,100, SMD ¼ 52 mm, spray cone

increase in inlet air swirl plays the dominant role in angle ¼ 801, swirl no. ¼ 0.76, T in
a ¼ 600 K, air–fuel ratio ¼ 60

reducing Zc and increasing ZII. However, at higher pressure Inlet pressure (kPa) Combustion efficiency Exergetic efficiency
the droplet penetration is as such low and hence the
favorable effect of enhanced mixing of fuel vapor in the gas 100 95.34 57.21
phase due to an increase in inlet air swirl plays the 300 93.56 61.53
600 91.32 71.82
prominent role in increasing the value of Zc and reducing 1000 83.31 79.93
the value of ZII. It has also been observed [64,65] (Table 2)
that an increase in the cone angle of spray increases the (b) Influence of inlet air temperature
combustion efficiency and decreases the second-law effi-
_ in
Inlet conditions: m a ¼ 0:1 kg=s, Rein ¼ 52,100, SMD ¼ 52 mm, spray cone
ciency. A higher spray cone angle results in a larger radial angle ¼ 801, swirl no. ¼ 0.76, pin ¼ 100 kPa, air–fuel ratio ¼ 60
dispersion and hence a better mixing of fuel vapor in the
gas phase. This causes an increase in the rate of combustion Inlet air temperature Combustion efficiency Exergetic efficiency
and accordingly in the total irreversibility in the process. (K)
Som and Sharma [66] predicted from an energy and 400 86.03 55.24
exergy balance of spray combustion process in a gas- 600 95.34 57.21
turbine combustor, that an increase in fuel volatility 800 99.53 55.60
increased the combustion efficiency only at higher
(c) Influence of inlet swirl number
pressures for any given inlet temperature and air swirl
(Table 3), while the second-law efficiency decreased with an _ in
Inlet conditions: m a ¼ 0:1 kg=s, Rein ¼ 52,100, SMD ¼ 52 mm, spray cone
increase in fuel volatility at any operating condition. The in
angle ¼ 801, T a ¼ 600 K, air–fuel ratio ¼ 60
physical explanations for these typical variations in Zc and
Inlet pressure Inlet swirl Combustion Exergetic
ZII, put forward by Som and Sharma [66] are as follows:
(kPa) number efficiency efficiency
The success for complete combustion depends on the
penetration of fuel droplets, their rate of vaporization, and 100 0.37 97.59 54.86
mixing of fuel vapor with air. At low pressures, for a given 100 0.76 95.34 57.21
temperature, all these three physical processes are relatively 600 0.37 87.24 75.70
600 0.76 91.32 71.82
fast and combustion efficiency is usually very high.
Therefore, the change in the rate of droplet vaporization (d) Influence of initial mean droplet diameter in injected spray
with fuel volatility does not make any marked influence in
combustion efficiency. However, on the other hand, when _ in
Inlet conditions: m a ¼ 0:1 kg=s, Rein ¼ 52,100, spray cone angle ¼ 801,
swirl no. ¼ 0.76, T in
a ¼ 600 K, pin ¼ 100 kPa, air–fuel ratio ¼ 60
the pressure in the combustion chamber is high, at a given
inlet temperature, there occur (i) a reduction in droplet Initial SMD (mm) Combustion Exergetic efficiency
penetration due to increased density of ambient air, and efficiency
(ii) a reduction in the rate of droplet vaporization due to a
34 94.37 59.63
decrease in fuel–air diffusivity with pressure. Therefore, for
52 95.34 57.21
a given fuel, an increase in combustion pressure for a fixed 67 95.61 53.43
inlet temperature always reduces the combustion efficiency. 96 94.11 51.13
Under this situation, the favorable effects of enhanced
droplet vaporization and its mixing with ambient air due to (e) Influence of spray cone angle
an increase in fuel volatility is felt sharply through a Inlet conditions: m_ in
a ¼ 0:1 kg=s, Rein ¼ 52,100, SMD ¼ 52 mm, swirl
marked increase in the combustion efficiency. The increase no. ¼ 0.76, T in
a ¼ 600 K, pin ¼ 100 kPa, air–fuel ratio ¼ 60
in second-law efficiency with pressure can be attributed to
simultaneous increase in flow availability of incoming air at Spray cone angle (1) Combustion Exergetic efficiency
efficiency
a high pressure and less process irreversibility due to
reduced droplet vaporization. 60 91.49 62.67
80 95.34 57.21
4.3. Solid fuel combustion 100 98.58 48.85

Coal is the most important solid fuel and is widely used much greater than the other fossil fuels. Most of the coal-
in generating electricity. It will be the principal fuel to meet fired power stations use pulverized coal for combustion.
the future demand of electricity since coal reserves are Coal is also used in the operation of a blast furnace, which
ARTICLE IN PRESS
S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376 373

Table 3
Influences of inlet pressure and swirl on combustion efficiency (%) and exergetic efficiency (%) in spray combustion for fuels with different volatilities [66]

_ in
Inlet conditions: m in
a ¼ 0:1 kg=s, Rein ¼ 52,400, SMD ¼ 52 mm, spray cone angle ¼ 801, T a ¼ 600 K, air–fuel ratio ¼ 60

Inlet pressure (kPa) Inlet swirl number Combustion efficiency (%) Exergetic efficiency (%)

n-Hexane Kerosene n-Dodecane n-Hexane Kerosene n-Dodecane

100 0.36 95.37 96.06 94.34 54.54 65.84 71.14


100 0.76 95.40 96.92 94.81 56.11 70.64 74.44
1000 0.36 91.14 82.92 64.43 74.04 83.27 86.43
1000 0.76 84.21 78.47 45.90 67.12 72.27 82.73

employs pulverized coal injection along with the blast air particle diameter with an initial decreasing trend of ZII
through its tuyere to reduce the coke feed rate. From the followed by an increasing one with the particle diameter.
view point of energy economy, an efficient process of coal The optimum design of the combustor is based on a trade-
combustion should be guided not only by the combustion off between Zc and ZII for an overall energy economy. The
efficiency of the process but also by its second-law relative weight of Zc and ZII to be assigned in the process of
efficiency. optimization depends on the relative savings in the cost of
Fundamental research in the field of coal combustion for energy quantity over the energy quality for a specific
the determination of the reaction rate parameters and application, which is a task of energy management in
modeling of reaction chemistry is going on for the last three practice.
decades. Both experimental and numerical works are Prins and Ptasinski [70], following the line of Dunbar
available and exhaustive reviews of all these works are and Lior [6], studied the exergy losses in the gasification
made in Smoot [67,68]. Som et al. [69] first attempted a and combustion process of solid carbon in a gasification
detailed second-law-based analysis in a cylindrical com- reactor by dividing the process into several subprocesses,
bustor burning pulverized coal particles. The full Navier–- like chemical reaction, internal thermal energy exchange
Stokes equations are solved along with the conservation of between reaction products and unburnt reactants, product
mass and energy, with the standard k–e model employed mixing, etc. The irreversibilities associated with the
for the solution of the turbulent quantities. A pdf-based individual subprocesses have been calculated using the
conserved scalar equation was solved for the species thermodynamic parameters for the isothermal and adia-
concentrations as well as the reaction rates. Following batic combustion of carbon in the reactor. The overall
the earlier spray model of Datta and Som [64], the coal efficiency is computed as the gain in exergy of the gas as a
particle tracking was done in a Lagragian frame and fraction of the change in exergy of the solid fuel (expressed
coupled with the Eulerian fluid flow through the carefully as the difference of exergy in the fuel input and the exergy
computed source terms. The exergy analysis is done of the unburned fuel). Alternately a term called efficiency
calculating the inlet and exit exergy components following defect is defined as the sum of the irreversibilities due to all
approach 1 given in Section 3.3. The second-law efficiency processes as a fraction of the exergy difference of the solid
for the combustion process is computed using Eq. (7). The fuel across the reactor. For stoichiometric combustion of
effect of variation in air temperature, airflow rate, particle carbon with air, exergy losses due to internal thermal
size and inlet swirl level of airflow on the second-law energy exchange (14–16% of expended exergy) are larger
efficiency were studied. The outcome of the studies are as than those due to the chemical reaction (9–11% of
follows: expended exergy). The overall exergetic efficiency in
An increase in air temperature decreases the combustion gasification process, employing partial combustion, is
efficiency for a shorter length of combustor, but increases found to be higher than that in combustion. In a
the combustion efficiency for a higher length of combustor. combustion process the fuel’s exergy is totally converted
The second-law efficiency follows a trend that bears an into the theromechanical exergy of the high-temperature
inverse relationship to that in combustion efficiency with product gas, while gasification retains a large part of
air temperature. At low values of inlet air swirl chemical exergy in the generated fuel gas. In gasification,
(S ¼ 0.0–0.32), an increase in SMD of coal particle the reaction remains very efficient while the exergy losses
decreases the combustion efficiency. At a higher value of related to internal thermal energy exchange (5–7% of
inlet air swirl (S ¼ 0.77) combustion efficiency increases expended exergy) are reduced due to the lower tempera-
with an increase in SMD from 50 to 95 mm, and thereafter ture. The efficiency in the gasification process can be
decreases with a further increase in SMD of coal particle improved by gasifying with oxygen instead of air, but the
from 95 to 145 mm. The second-law efficiency always irreversibilities incurred in separating oxygen from air
increases with an increase in the particle diameter, whereas, nullify this advantage. In order to maximize the chemical
at high swirl of S ¼ 0.77, this trend shows an optimum exergy present in the product gas, for oxygen-blown
ARTICLE IN PRESS
374 S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376

gasification of fuels like solid carbon, it was advised to potential exergy, strain exergy and kinetic exergy are too
moderate the temperature with steam and operate between small and can be ignored. Consequently, the major exergy
1200 and 1400 K for atmospheric pressure and components were reported to be thermal and chemical.
1300–1500 K for elevated pressures. In this way, up to The thermomechanical and chemical exergy fields and
75% of the exergy contained in solid fuels can be converted the total exergy field as reported by the authors are shown
into chemical exergy of carbon monoxide and hydrogen. in Figs. 14a–c. About 30% of the fuel exergy is found to be
Lior [34] presented the exergy analysis in a Radiatively/ destroyed in the combustion process. The maximum exergy
Conductively Stabilized Pulverized Coal Combustor destruction was found in the thin flame zone, and only
(RCSC) earlier modeled by Kim and Lior [71,72]. The about 10% of the destruction was found to occur down-
analysis used the computer simulation results, which stream to the flame due to heat transfer to the wall and exit.
consisted of the solution of the conservation of mass, Increasing the air inlet temperature was found to slightly
momentum, energy and species conservation equations decrease the exergy efficiency.
with the standard k–e equations. The radiative transfer
equation was solved using spherical harmonics method. 5. Conclusion
The particle trajectories were solved in the Lagrangian
frame. A 13-equation chemical kinetic model for reaction The optimum operating conditions of a combustor in
and separate models for devolatilization, volatile combus- practice depend on an overall fuel economy and other
tion were used. The solution gives three-dimensional desirable combustion characteristics like combustion
distribution of gas, particle and wall temperature, radiation chamber wall temperature and emissions. However, the
intensity, gas and particle velocity and species concentra- important consideration of fuel economy for a combustor
tions. These results are used for the spatial determination of a power-producing unit pertains to the trade-off between
of all the components of exergy. It was found from the the efficient conversion of energy quantity and minimum
order of magnitude of different components of exergy that destruction of energy quality (exergy). This is determined

24000
/ kg coal

28000
18000
coal

24000 28000
21500
Exergy, kJ

Exergy, kJ / kg

12000
18000 15000 21500
6000
12000 8500 15000
0
11 2000
9 6000 11 8500
9
7
0 7 2000
5 5 127
127 109
3 91 109 3 91
73 55 73
37 55 37
1
1
19 Z/R 1 1
19 Z/R

51000.0

51000.0
Exergy, kJ / kg coal

42000.0

15000.0
9 33000.0
7
5
3 24000.0
1
1 19 15000.0
37 55 72
91
Z/R 109 127

Fig. 14. (a) Thermomechanical exergy distribution in a pulverized coal combustor [34]. (b) Chemical exergy distribution in a pulverized coal combustor
[34]. (c) Total exergy distribution in a pulverized coal combustor [34].
ARTICLE IN PRESS
S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376 375

from the knowledge of the relationship of combustion [11] Bejan A, Tsatsaronis G, Moran M. Thermal design and optimization.
efficiency and exergetic efficiency with the operating New York: Wiley; 1996.
parameters. This information are furnished by the funda- [12] Yilmaz M, Sara ON, Karsli S. Performance evaluation criteria for
heat exchangers based on second law analysis. Exergy Int J 2001;1(4):
mental studies on the identification of irreversibilities and
278–94.
subsequent exergy analysis in a combustion process, which [13] Rosen MA, Dincer I. Survey of thermodynamic methods to improve
has been reviewed in the present paper. The major the efficiency of coal-fired electricity generation. J Power Energy Proc
observations relating to the reduction of thermodynamic Inst Mech Eng 2003;217A:63–73.
irreversibilities in combustion processes are as follows: [14] Yasni E, Carrington CG. The role for exergy auditing in a thermal
power station. HTD Am Soc Mech Eng 1987;80:101–9.
[15] Habib MA, Said SAM, Al-Zaharna I. Optimization of reheat
 Chemical reaction and physical transport processes are pressures in thermal power plants. Energy—Int J 1995;20:555–65.
the sources of irreversibilities in combustion. In many [16] Habib MA, Said SAM, Al-Bagawi JJ. Thermodynamic performance
situations, the major part played among all physical analysis of the Ghazlan power plant. Energy—Int J 1995;20:1121–30.
processes is the internal thermal energy exchange. [17] Gaggioli RA, Yoon JJ, Patulski SA, Latus AJ, Obert EF. Pinpointing
 All combustion reactions are thermodynamically irre- the real inefficiencies in power plants and energy systems. Proc Am
Power Conf 1975;37:656–70.
versible. However, the rate of exergy destruction by
[18] Taniguchi H, Mouri K, Nakahara T, Arai N. Exergy analysis on
chemical reaction can be reduced if the flame tempera- combustion and energy conversion processes. Energy 2005;30:111–7.
ture is kept high. It can be done by oxygen enrichment [19] Sengupta S, Datta A, DuttaGupta S. Exergy analysis of a coal based
of air through an exergy efficient method. 210 MW thermal power plant. Int J Energy Res 2007;31(1):14–28.
 The most important way of keeping exergy destruction [20] Kwak HY, Kim DJ, Jeon JS. Exergetic and thermoeconomic analyses
in combustion within limit is to reduce the irreversibility of power plants. Energy 2003;28:343–60.
in heat conduction due to internal mixing. Combustion [21] Horlock JH, Young JB, Manfrida G. Exergy analysis of modern
fossil-fuel power plants. Trans ASME J Eng Gas Turbines Power
should be controlled to occur with less temperature 2000;122:1–7.
gradient in the combustor. This can be attained by air [22] Harvey S, Kane N. Analysis of a reheat gas turbine cycle with
preheating, fuel–air staging, and controlling the jet chemical recuperation using aspen. Energy Convers Manage
velocities. 1997;38(15–17):1671–9.
 For the design and development of energy and exergy [23] Anheden M, Svedberg G. Exergy analysis of chemical looping
efficient combustion systems, further fundamental stu- combustion systems. Energy Convers Manage 1998;39(16–18):
1967–80.
dies are required to understand the influences of
[24] Ertesvag IS, Kvamsdal HM, Bolland O. Exergy analysis of a gas
turbulence and vorticity on entropy production in turbine combined cycle power plant with precombustion CO2
different types of flames and also the influence of capture. Energy 2005;30:5–39.
pressure on exergetic efficiency of combustion process in [25] Caton JA. On the destruction of availability (exergy) due to
high-pressure flames. combustion processes- with specific application to internal combus-
 Finally, the work extraction devices should be properly tion engines. Energy 2000;25:1097–117.
[26] Kanoglu M, Isik SK, Abusoglu A. Performance characteristics of a
designed to extract the maximum exergy contained in
diesel engine power plant. Energy Convers Manage 2005;46:
the product gas. 1692–702.
[27] Caton JA. A review of investigations using the second law of
thermodynamics to study internal-combustion engines. In: SAE
paper no. 2000-01-1081. Society of Automotive Engineers, 2000.
References [28] Primus RJ, Flynn PF. The assessment of losses in diesel engines using
second law analysis. In: Gaggioli RA, editor. Computer-aided
[1] Derived from the website of Energy Information Administration engineering of energy systems, AES-vol. 2–3. American Society of
(EIA) at /www.eia.doe.govS. Mechanical Engineers, Advanced Energy Systems Division, Decem-
[2] Rant Z. Exergy, a new word for technical available work. Forsch Ing
ber, 1986.
Wes 1956;22(1):36–7 [in German].
[29] Alkidas AC. The application of availability and energy balances to a
[3] Rosen MA, Dincer I. Exergy as the confluence of energy, environ-
diesel engine. Trans ASME J Eng Gas Turbines Power 1988;110:
ment and sustainable development. Exergy Int J 2001;1(1):3–13.
462–9.
[4] Rosen MA. Clarifying thermodynamic efficiencies and losses via
[30] Alkidas AC. The use of availability and energy balances in diesel
exergy. Exergy Int J 2002;2:3–5.
engines. In: SAE paper no. 890822, Society of Automotive Engineers,
[5] Rosen MA. Exergy conservation: an alternative to conserving the
already conserved quantity energy. Exergy Int J 2002;2:59–61. 1989.
[6] Dunbar WR, Lior N. Sources of combustion irreversibility. Combust [31] Caton JA. Operating characteristics of a spark-ignition engine using
Sci Technol 1994;103:41–61. the second law of thermodynamics: effects of speed and load. In: SAE
[7] Bejan A. Second-law analysis in heat transfer and thermal design. paper no. 2000-01-0952, Society of Automotive Engineers, 2000.
Adv Heat Transfer 1982;15. [32] Rakopoulos CD, Giakoumis EG. Second law analysis applied to
[8] Bejan A. Entropy generation through heat and fluid flow. New York: internal combustion engines operation. Prog Energy Combust Sci
Wiley; 1982. 2006;32:2–47.
[9] Bejan A. Entropy generation minimization. New York: CRC Press; [33] Rasul MG, Tanty BS, Mohanty B. Modelling and analysis of blast
1995. furnace performance for efficient utilization of energy. Appl Therm
[10] Bejan A. Entropy generation minimization: the new thermodynamics Eng 2007;27:78–88.
of finite-size devices and finite-time processes. J Appl Phys 1996;79: [34] Lior N. Irreversibility in combustion. Invited Keynote Paper. Proc
1191–218. ECOS, 2001, p. 39–48.
ARTICLE IN PRESS
376 S.K. Som, A. Datta / Progress in Energy and Combustion Science 34 (2008) 351–376

[35] Lior N, Sarmiento-Darkin W, Al-Sharqawi HS. The exergy fields in [56] Yapıcı H, Kayatas N, Albayrak B, Basturk G. Numerical calculation
transport processes: their calculation and use. Energy 2006;31: of local entropy generation in a methane–air burner. Energy Convers
553578. Manage 2005;46:1885–919.
[36] Borman GL, Ragland KW. Combustion engineering. New York: [57] Yapıcı H, Kayatas N, Albayrak B, Basturk G. Numerical study on
McGraw-Hill; 1998. local entropy generation in a burner fueled with various fuels. Heat
[37] Westbrook CK, Dryer FL. Chemical kinetic modeling of hydro- Mass Transfer 2005;41:519–34.
carbon combustion. Prog Energy Combust Sci 1984;10:1–57. [58] Dash SK, Sengupta SP, Som SK. Transport processes and associated
[38] Moran MJ, Shapiro HN. Fundamentals of engineering thermody- irreversibilities in droplet evaporation. AIAA J Thermo Phys Heat
namics. 4th ed. Singapore: Wiley; 2000. Transfer 1991;5(3):366–73.
[39] Adebiyi GA. Limits of performance for alternate fuel energy to [59] Hiwase SD, Datta A, Som SK. Entropy balance and exergy analysis
mechanical work conversion systems. ASME J Energy Resources
of the process of droplet combustion. J Phys D: Appl Phys 1998;31:
Technol 2006;128:229–35.
1601–10.
[40] Turns SA. An introduction to combustion. 2nd ed. New York:
[60] Dash SK, Som SK. Transport processes and associated irreversi-
McGraw-Hill; 2000.
bilities in droplet combustion in a connective medium. Int J Energy
[41] Datta A, Som SK. Energy and exergy balance in a gas turbine
Res 1991;15(7):603–19.
combustor. J Power Energy—Proc Inst Mech Eng 1999;213A:23–32.
[42] Hirschfelder JO, Curtiss CF, Bird RB. Molecular theory of gases and [61] Puri IK. Second law analysis of convective droplet burning. Int J
liquids. New York: Wiley; 1954. Heat Mass Transfer 1992;35:2571–8.
[43] Teng H, Kinoshita CM, Masutani SM, Zhou J. Entropy generation [62] Som SK, Mitra AK, Sengupta SP. Second law analysis of spray
in multicomponent reacting flows. Trans ASME J Energy Resources evaporation. ASME J Energy Resources Technol 1990;112:130–5.
Technol 1998;120:226–32. [63] Som SK, Dash SK. Thermodynamics of spray evaporation. J Phys D:
[44] Arpaci VS. Radiative entropy production—lost heat into entropy. Int Appl Phys 1993;26(4):574–84.
J Heat Mass Transfer 1987;30:2115–23. [64] Datta A, Som SK. Thermodynamic irreversibilities and second law
[45] San JY, Worek WM, Lavan Z. Entropy generation in convective heat analysis in a spray combustion process. Combust Sci Technol 1999;
transfer and isothermal convective mass transfer. Trans ASME J 142:29–54.
Heat Transfer 1987;109:647–52. [65] Datta A. Hydrodynamics of swirl spray atomizer and thermal
[46] San JY, Worek WM, Lavan Z. Entropy generation in combined heat dynamics of gas turbine combustion. PhD thesis, Indian Institute of
and mass transfer. Int J Heat Mass Transfer 1987;30:1359–69. Technology, Kharagpur 1998.
[47] Sun ZF, Carrington CG. Application of non-equilibrium thermo- [66] Som SK, Sharma NY. Energy and exergy balance in the process of
dynamics in second law analysis. Trans ASME J Energy Resource spray combustion in a gas turbine combustor. ASME J Heat Transfer
Technol 1991;113:33–9. 2001;124:828–36.
[48] Carrington CG, Sun ZF. Second law analysis of combined heat and [67] Smoot LD. A decade of combustion research. Prog Energy Combust
mass transfer phenomena. Int J Heat Mass Transfer 1991;34:2767–73. Sci 1997;23:203–32.
[49] Gyftopoulos EP, Beretta GP. Entropy generation rate in a chemically [68] Smoot LD. Modeling of coal combustion processes. Prog Energy
reacting system. ASME J Energy Resources Technol 1993;115: Combust Sci 1984;10:229–72.
208–12.
[69] Som SK, Mandal SS, Dash SK. Energy and exergy balance in the
[50] Arpaci VS, Selamat A. Entropy production in flames. Combust
process of pulverized coal combustion in a tubular combustor.
Flame 1988;73:251–9.
ASME J Heat Transfer 2005;127:1322–33.
[51] Datta A. Entropy generation in a confined laminar diffusion flame.
[70] Prins MJ, Ptasinski KJ. Energy and exergy analyses of the oxidation
Combust Sci Technol 2000;159:39–56.
and gasification of carbon. Energy 2005;30:982–1002.
[52] Datta A. Effects of gravity on structure and entropy generation of
confined laminar diffusion flames. Int J Therm Sci 2005;44:429–40. [71] Kim C, Lior N. Combined-mode conjugate heat transfer in a
[53] Stanciu D, Isvoranu D, Marinescu M, Gogus Y. Second law analysis radiatively/conductively stabilized pulverized coal combustor. ASME
of diffusion flames. Int J Appl Thermodynamics 2001;4:1–18. paper 93-WA/HT-37, ASME winter annual meeting, New Orleans,
[54] Nishida K, Takagi T, Kinoshita S. Analysis of entropy generation LA, 1993.
and exergy loss during combustion. In: Proceedings of the 29th [72] Kim C, Lior N. A numerical analysis of NOx formation and control
symposium (international) of the Combustion Institute, vol. 29, 2002, in radiatively/conductively stabilized pulverized coal combustors.
p. 869–74. J Chem Eng 1998;71:221–31.
[55] Datta A, Leipertz A. Thermodynamic optimization of a laminar [73] Daw SC, Chakravarthy K, Conklin CJ, Graves RL. Minimizing
diffusion flame. In: Proceedings of first heat transfer fluid mechanics destruction of thermodynamic availability in hydrogen combustion.
and thermodynamics conference, vol. 1, South Africa, 2002, p. 111–6. Int J Hydrogen Energy 2006;31:728–36.

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