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original
he process industries are ex
tensive users of energy. But it
is now clearly established that
a large amount of this energy
is wasted, essentially in the
form of heat rejected to the environ
ment through gaseous or liquid ef
fluents. The temperature level of this
heat makes it of no use by the process;
and at the same time, in many cases,
it cannot be economically upgraded.
Examples of industries rejecting con
siderable thermal energy include:
thermal power plants, metallurgical
processing, the cement industry, pulp
and paper, and petrochemicals. Table
1 gives typical exhaust temperatures
for some such industries.
On the basis of the second law of
thermodynamics, the quality of an
energy source is determined by its
ability to perform work. In the spe
cialized literature, this work potential
is referred to as availability, or more
precisely “available energy” or exergy.
From this standpoint, heat (thermal
energy) is considered to be the most
degraded form of energy.
A simplified approach to evalu
ate the exergy content of a hot waste
stream is presented here. The objective
is to provide engineers a means to eas
ily estimate the amount of useful en
ergy they may recover from industrial
heat exhausts. Such energy can be
used, for example, to drive a turbine for
onsite production of electricity. Some of
the new and emerging technologies for
converting waste heat into work are
also briefly described. Many of these
technologies are already on the market
or on the verge of commercialization.
The concept of exergy
Exergy is a thermodynamic property
that was first introduced in the mid
1950s as a measure of the capability of
a hot stream to produce useful work.
Exergy is related to the wellknown
thermodynamic properties enthalpy
and entropy through the equation:
Ex H H T S S = − ( ) − ⋅ − ( )
0 0 0
(1)
where H is the specific enthalpy of the
stream, S the specific entropy of the
stream, and T is the temperature in
Kelvins. The subscript 0 indicates a
reference condition, which usually cor
responds to the environment contain
ing or surrounding the system.*
Several properties of exergy can be
noted with the definition of Equation
(1). The exergy content of the stream
is a fraction of the enthalpy content
of the stream. This enthalpy content
alone does not give any indication of
the potential to extract some work
from the heat resource. Equation (1)
also shows that a heat resource, re
gardless of its amount, carries no
work potential (zero exergy) when it is
at the same (thermal, mechanical and
chemical) conditions as its surround
ing. In other words, if a stream is in
equilibrium with its surroundings, it
can produce no work. In fact, this rep
resents the main difference between
exergy and Gibbs free energy which is
a property of the stream, regardless of
the surrounding environment.
Exergy variation between an initial
state (subscript i) and a final state
(subscript f) is therefore:
∆Ex H H T S S
f i f i
= 
( )
− ⋅ −
( ) 0
(2)
If Equations (1) and (2) are writ
ten on a molar basis, for instance, the
maximum power recoverable via the
conversion of this heat resource from
Condition i to Condition f is:
W F Ex
E
⋅ ∆
(3)
where F is the molar flow rate.
For an ideal mixture of different
components j, enthalpy can be calcu
lated as the sum of the enthalpies of
the mixed components:
H x H
j
j
j
⋅ ∑
(4)
where x
j
is molar fraction of compo
nent j and H
j
is its specific enthalpy.
In the case of entropy, we cannot
assume here that the entropy of such
mixtures is the sum of entropies of the
mixed components as it is the case for
enthalpy. Instead, the following equa
tion should be used for ideal mixtures
[1]:
S x S R x x
j
j
j j
j
j
⋅ − ⋅ ⋅
( ) ∑ ∑ ln
(5)
Therefore, Equations (4) and (5) can
be used to calculate the enthalpies
and entropies needed in Equation (2)
for determining the exergy change for
ideal mixtures.
For the general cases of nonideal
gases, chemicals, and complex mix
tures, one may build a computer pro
gram or use a commercial software.
Feature Report
40 CHEMICAL ENGINEERING WWW.CHE.COM OCTOBER 2006
Get the Most
Out of Waste Heat
Exergy analysis reveals the amount of useful work
you can get from a warm exhaust stream
Engineering Practice
Raynald Labrecque
and Kiari Goni Boulama
Institut de Recherche d’Hydro
Québec (Laboratoire des
Technologies de l’Énergie)
* The key reference conditions for a chemical plant
would be, for example, ambient temperature and
pressure. Other factors, such as humidity, concen
trations (of N
2
, O
2
in air, or salts in a surrounding
river or sea), altitude (gravity) can have an impact
on the numerical value of the exergy, and must be
properly specified for a careful analysis.
Many commercial process simulators,
including Aspen Plus, ChemCad, and
Prosim Plus, are well equipped for
calculating the thermodynamic prop
erties (such as H and S) of pure sub
stances, mixtures and solutions (ideal
or nonideal). Then Equations (1) and
(2) may be straightforwardly applied
to obtain the exergy of a stream or the
exergy change experienced between
two states.
Some examples
Thus far, we have demonstrated a way
to easily calculate the maximum work
potential (Ex) one may extract from a
given heat resource by using very sim
ple mathematics. These equations may
also be used to construct a brand new
generation of thermodynamic correla
tions, tables and diagrams [2] for vari
ous working fluids of interest. In the
following, some examples of the calcu
lations and applications are presented.
Example 1. Ideal gas mixtures: In
order to illustrate how easy it can be to
calculate the exergy of a fluid stream,
let us first consider the case of ideal
gas mixtures. From the definition of
the heat capacity at constant pres
sure, C
p
, we can write the enthalpy
differential of an ideal gas as:
dH C dT
p
⋅
(6)
Furthermore, for a constant pressure
process and nonreacting flow, the en
tropy differential is:
dS
dH
T
C
T
dT
p
⋅
(7)
Therefore, the specific exergy (rela
tive to the reference 0) of the gas is
given by:
Ex dH T dS
C dT T
C
T
dT
T
T
p
T
T
p
T
T
− ⋅ ( )
⋅ − ⋅
∫
∫ ∫
0
0
0
0 0
(8)
For the case where C
p
is indepen
dent of temperature, the integration
of Equation (8) yields:
(9) Ex C T T T
T
T
p
⋅ − ( ) − ⋅

(
'
·
J
J
]
]
]
]
0 0
0
ln
With the assumption of constant
pressure kept in mind, Equation (9)
can be used only if the pressure of the
hot effluent is the same as the pres
sure of the surroundings.
Equation (9) clearly shows one of
the key properties of exergy: it de
creases as the flow temperature ap
proaches that of the reference medium
(or surroundings) and it completely
vanishes (no more work availability)
when the two temperatures are equal
(T = T
0
).
It is also worth noting that Equation
(9) can be derived by starting with the
the Carnot efficiency,
c
; the relation
ship can be written as:
dEx dH
c
⋅ η
(10)
Replacing
c
by the expression (1
– T
C
/T
H
), where the subscripts refer
to the hot and cold reservoir, gives:
dEx C dT
T
T
p
⋅ ⋅ −

(
'
·
J
J 1
0
(11)
which can readily be integrated to re
trieve Equation (9).
Equation (9) applies only for ideal
gases at the same pressure as the
reference pressure. A more general
expression can be derived when the
gas pressure is different from the ref
erence pressure [3]:
Ex C T T T
T
T
RT
P
P
p
⋅ − ( ) − ⋅

(
'
·
J
J
]
]
]
]
+ ⋅

(
'
·
J
J
0 0
0
0
0
ln
ln
(12)
In reality, C
p
depends on temperature,
and this fact becomes important espe
cially when large temperature changes
are involved. In these cases, simple
polynomial relations are often proposed
in order to express this temperature de
pendence, such as the following:
C a bT cT dT
p
+ + +
2 3
(13)
Values of parameters a, b, c and d for
some common gases may be found in
Reference [4].
Introducing Equation (13) into
Equation (8) and integrating yields
the following expression:
(14)
Ex a T T
b
T T
c
T T
d
T T
T a
T
T
b T T
c
T T
d
T T
⋅ − ( ) + ⋅ −
( )
+ ⋅ −
( )
+ ⋅ −
( )
− ⋅ ⋅

(
'
·
J
J
+ ⋅ − ( ) + ⋅
−
( )
+ ⋅ −
( )
]
]
]
0
2
0
2
3
0
3 4
0
4
0
0
0
2
0
2 3
0
3
2
3 4
2
3
ln
We can see that the exergy content
of a waste stream can be calculated
quite easily in the case of ideal mix
tures. Figure 1 presents enthalpy and
exergy as functions of temperature
for nitrogen at ideal state and at a
reference pressure. Enthalpy is cal
culated as C
p
·(T – T
0
) and exergy is
CHEMICAL ENGINEERING WWW.CHE.COM OCTOBER 2006 41
TABLE 1. TYPICAL EXHAUST TEMPERATURES
FOR SOME SELECTED INDUSTRIAL PROCESSES
Industries Effluent temperature, °C Type of effluent
Petrochemical and petroleum
refining plants
150 – 300 Liquid, gas
Incineration plants 150 – 430 Gas
Natural gas liquification
plants
150 – 260 Gas
Metallurgical plants 100 – 350 Liquid, gas
Pulp and paper mills 80 – 100 Liquid, gas
Drying systems 90 – 370 Liquid, gas
Ceramic manufacturing
plants
150 – 450 Gas
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FIGURE 1. Enthalpy and exergy of ni
trogen as a function of temperature, for
reference conditions of 25°C and 1 atm
calculated using Equation (14). The
reference conditions are temperature
of 25°C and standard atmospheric
pressure. Figure 2 shows how the
ratio of exergy to enthalpy varies
for nitrogen. For example, at 100°C,
Ex/H is 0.11. This means that for
a heat resource consisting of 100°C
hot stream of nitrogen, a maximum
of 11% of the total enthalpy is recov
erable as shaft work.
Example 2. Incompressible fluids:
For incompressible liquids, enthalpy
is defined in quite a similar way as
for ideal gases [Equation (6)], so that
a similar reasoning as the one con
ducted above can be done to yield an
equation similar to Equation (9). A
more general expression taking into
account the pressure effect is:
Ex C T T T
T
T
V P P
⋅ − ( ) − ⋅

(
'
·
J
J
]
]
]
]
+ ⋅ − ( )
0 0
0
0
ln
(15)
where C is the specific heat of the
liquid and V is the specific volume.
Example 3. Saturated steam and
hot bubbling water: As for the
ideal gases above, the enthalpy and
entropy data for steam and bubbling
water are wellknown. Figures 3 and
4 present enthalpy and calculated
exergy respectively for saturated
steam and boiling water (saturated
liquid water), with the reference con
dition being saturated liquid water
at 25°C. These two graphs confirm
that, for a fluid stream hotter than
the environment (T > T
0
), higher
temperature means higher exergy.
Figure 5 shows the evolution of the
exergy to enthalpy ratio with respect
to temperature, for both saturated
steam and hot boiling water. Here
one observes that the ratio Ex/H
increases with temperature. At a
temperature of around 100°C, the
theoretical exergy/enthalpy ratio is
close to 0.17 for steam and 0.11 for
hot bubbling water.
It should be noted that, for tem
peratures below 100°C, the effect
of pressure on the exergy content
is insignificant for liquid water. For
instance, the exergy of hot water at
80°C and 1 atm is nearly the same as
that of hot water at 80°C and satura
tion pressure.
From these three examples, we
have shown that it is theoretically
possible to use hot gases, low pres
sure steam or hot water as a source
of useful work, which in turn, could
be used for producing electricity. If
useful heat cannot be recovered from
a hot waste stream for use elsewhere
in the plant, at least some recover
able useful work could be produced
out of such waste streams, even for
temperatures as low as 100°C. In
the next section, we will briefly dis
cuss some technologies available, or
being developed, for the conversion
of low grade heat resources to elec
tricity.
Conversion techniques
Numerous types of apparatus have
been proposed for the conversion
of lowtemperature heat into use
ful work using the thermodynamic
cycles of heat engines. It goes with
out saying that the total power out
put of such systems will be lower
than the available work potential.
In fact, the efficiency of these cycles
depends on the nature of the heat
source and heat sink, as well as
that of the conversion device itself
together with all its components. We
can define an efficiency term for the
recovery of exergy:
(16)
η
e
net
W
Ex
∆
where W
net
is the net work produced
and ΔEx is the exergy variation of a
hot stream transferring heat to the
system or device (through a heat
exchanger). Exergy efficiencies as
high as 70% are conceivable.
The use of the Rankine cycle with
steam as working fluid for the pro
duction of electricity is wellknown,
but is not appropriate in the case
of lowtemperature (< 240°C) heat
sources. Alternatives have therefore
been proposed, such as the organic
Rankine cycle (ORC) and the Kalina
cycle.
The idea behind ORC is the
use of working fluids that have a
higher vapor pressure than water.
Refrigerants such as R11, R113,
Engineering Practice
42 CHEMICAL ENGINEERING WWW.CHE.COM OCTOBER 2006
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FIGURE 3. Enthalpy and exergy of
steam as a function of temperature,
for reference conditions:
saturated liquid water at 25°C
FIGURE 4. Enthalpy and
exergy of boiling water,
for reference conditions:
saturated liquid water at 25°C
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FIGURE 2. The ratio of
exergy/enthalpy for nitrogen
as function of temperature
(T
0
= 25°C, P at reference level)
R114 have been proposed as ORC
working fluids [5]. Many hydrocar
bons, such as isobutene, isopentane
and cyclopentane, are promising
alternative fluids [6]. An advan
tage of using hydrocarbons is that,
in many cases, they are “drying
fluids,” which means that there
is no condensation occuring dur
ing the expansion process for the
production of work. Condensation
is highly detrimental to turbine
blades and, in conventional Ran
kine cycles, steam is superheated
before entering the turbine in order
to avoid this problem. This extra
heat expense (vapor superheat)
is eliminated when using an ORC
with a dry fluid [7]. This technology
is now mature and well established
throughout the world.
Ammonia (R717) has been pro
posed as an alternative working
fluid, again because it has a much
higher vapor pressure compared
to water at a given temperature.
Furthermore, since ammonia has
a molecular weight close to that of
water, conventional steam turbine
equipment can be used. The princi
pal drawback with ammonia is with
regard to safety (toxicity), and the
fact that it is a wetting molecule (it
condenses during expansion). The
technology is on the verge of com
mercialization [8].
Another interesting thermody
namic cycle strongly considered for
utilizing lowtemperature waste heat,
and which is on the verge of commer
cialization, is the Kalina cycle. This
cycle is based on the use of an am
moniawater mixture as a working
fluid [9]. One of its interesting fea
tures is its flexibility; the composi
tion of the working fluid can be pur
posefully modulated to accommodate
the available heat resource. Another
remarkable feature related to the
Kalina cycle is that the temperature
of the working fluid increases during
the boiling process, following more
closely the temperature decrease of
the heat source. Because of this bet
ter match between the temperatures
of the two streams, less irreversibility
is to occur.
Final remarks
In the industrial sector, a lot of heat
is simply discarded into the environ
ment because it is considered as of no
value or not useful for a specific pro
cess. A hot stack gas, a residual low
pressure steam or even a hot waste
water stream all have the potential
to produce some useful work. This
potential can easily be calculated for
any kind of stream, as shown by the
examples above.
Apart from computing the frac
tion of the thermal energy that can
be converted to motive power, exergy
analysis can also be used to improve
the efficiency of a process or to pin
point and quantify imperfections for
a given process [10, 11]. However,
higher exergy efficiency involves
moreexpensive design so that a bal
ance should be made between capital
cost and operating efficiency.
Finally, the integration of exergy
analysis in the industrial sector
contributes not only for better en
ergy efficiency, but also for a better
environment. ■
Edited by Gerald Ondrey
CHEMICAL ENGINEERING WWW.CHE.COM OCTOBER 2006 43
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FIGURE 5. The ratio of exergy to
enthalpy for steam and boiling water,
for reference conditions:
saturated liquid water at 25°C
Authors
Raynald Labrecque is a
research scientist working
for Institut de Recherche
d’HydroQuébec, at LTE labo
ratory (Laboratoire des Tech
nologies de l’Énergie, 600 De
la Montagne Ave., Shawin
igan, Province of Quebec,
Canada, G9N 7N5; Phone:
8195391400, ext. 1452; Fax:
8195391409; Email: la
brecque.raynald@lte.ireq.ca).
He holds B.S. and M.S. degrees in chemical engi
neering from Laval University (Québec City). For
the last 24 years he has been involved as a sci
entist or project leader in many projects regard
ing efficient use of electricity in industry and in
developing and demonstrating of new processes
based on the use of electricity or electrotech
nologies. His professional membership includes:
Ordre des Ingénieurs du Québec and Association
Québécoise pour la Maîtrise de l’Énergie. His
main area of activities includes process analysis,
electrosynthesis and electrochemical processes,
energyefficient electrotechnologies, thermo
chemical energyconversion processes (such
as gasification, pyrolysis and combustion), and
thermodynamic processes for energy conversion.
He is co inventor for two patents and has an
other patent pending. He is author or coauthor
of more then fifty publications and more than 75
HydroQuébec technical reports.
Kiari Goni Boulama is a junior scientist work
ing for Institut de Recher
che d’HydroQuébec, at LET
(Laboratoire des Technologies
de l’Énergie, same address
as above; Phone: 819 539
1400, ext. 1393; Fax: 819 539
1409; Email: goniboulama.
kiari@lte.ireq.ca) a group of
the Institut de Recherche
d’HydroQuebec (IREQ). He
holds a B.Eng. in energy en
gineering from the National
School of Engineering of Monastir (Tunisia)
and a Ph.D. in mechanical engineering from the
University of Sherbrooke (Québec). He has been
awarded a postdoctoral fellowship by the Natu
ral Sciences and Engineering Research Council
of Canada (NSERC), the LTE being the host in
stitution. Goni Boulama’s scientific interests are
heat and masstransport processes, thermody
namics and energy conversion. He is author of
several articles published in technical journals
and international conference proceedings.
References
1. Wall, G., Exergy Flows in Industrial Pro
cesses, Energy, Vol. 13, No. 2, p. 198, 1988.
2. Bejan, A., Blending Geometry with Numeri
cal Computation: Charts for Enthalpy, Abso
lute Entropy, and Flow Exergy of 12 Gases at
Low Pressures, Int. J. Heat and Fluid Flow,
Vol. 9, No. 22, pp. 251–253, 1988.
3. ibid.
4. Reid, R.C., Prauznitz J.M., and Poling, B.E.,
“The Properties of Gases & Liquids,” 4th ed.,
McGrawHill Book Co., pp. 657, 732, 1987.
5. Larjola, J., Electricity from Industrial Waste
Heat Using Highspeed Organic Rankine
Cycle (ORC), Int. J. Production Economics,
Vol. 41, pp. 227–235, 1995.
6. Riffat, S.B. and Nguyen, V.M., Combined
Heat and Power System Driven by Low
Grade Heat Sources, Int. J. of Ambient En
ergy, Vol. 19, No. 4, pp.181–186, 1998.
7. Hung TzuChen, Waste Heat Recovery of Or
ganic Rankine Cycle Using Dry Fluids, En
ergy Conversion and Management, Vol. 42,
pp. 539–553, 2001.
8. Use of waste heat to make electricity, with
out fuel, Chem. Eng., March, p. 16, 2004.
9. Erickson, D.D.C. and others, HeatActivated
DualFunction Absorption Cycle, ASHRAE
Transactions, Vol. 110, No. 1, pp. 515–525,
2004.
10. Bejan A., “Advanced Engineering Thermo
dynamics,” 2nd ed., Chapter 5, pp. 217–238,
1997.
11. Wall, G., Exergy Flows in Industrial Pro
cesses, Energy, Vol. 13, No. 2, pp. 197–208,
1988.
c and d for some common gases may be found in Reference [4]. These equations may also be used to construct a brand new generation of thermodynamic correlations. let us first consider the case of ideal gas mixtures. Then Equations (1) and (2) may be straightforwardly applied to obtain the exergy of a stream or the exergy change experienced between two states. TYPICAL EXHAUST TEMPERATURES FOR SOME SELECTED INDUSTRIAL PROCESSES Industries Petrochemical and petroleum refining plants Incineration plants Natural gas liquification plants Metallurgical plants Pulp and paper mills Drying systems Ceramic manufacturing plants Effluent temperature. Equation (9) clearly shows one of the key properties of exergy: it decreases as the flow temperature approaches that of the reference medium (or surroundings) and it completely vanishes (no more work availability) when the two temperatures are equal (T = T0). Cp depends on temperature. c. and this fact becomes important especially when large temperature changes are involved. Ideal gas mixtures: In order to illustrate how easy it can be to calculate the exergy of a fluid stream. Enthalpy and exergy of nitrogen as a function of temperature. where the subscripts refer to the hot and cold reservoir. the relationship can be written as: dEx = dH ⋅ ηc In reality. In these cases. mixtures and solutions (ideal or nonideal). are well equipped for calculating the thermodynamic properties (such as H and S) of pure substances.��������������������������� TABLE 1. It is also worth noting that Equation (9) can be derived by starting with the the Carnot efficiency. Introducing Equation (13) into Equation (8) and integrating yields the following expression: Ex = a ⋅ (T − T0 ) + b ⋅ T 2 − T02 2 + c ⋅ T 3 − T03 + d ⋅ T 4 − T04 3 4 T −T0 ⋅ a ⋅ ln + b ⋅ (T − T0 ) + c ⋅ 2 T0 ( ) ( ( ) ) (14) (6) (10) Furthermore. b. gas Gas ����� ����� ����� ����� ����� ����� � � ������ �������� �� ��� ��� ��� ��������������� ��� FIGURE 1. Enthalpy is calculated as Cp·(T – T0) and exergy is 41 CHEMICAL ENGINEERING WWW. In the following. the specific exergy (relative to the reference 0) of the gas is which can readily be integrated to retrieve Equation (9). Cp. some examples of the calculations and applications are presented. gas Liquid. the entropy differential is: Cp dS = dH = ⋅ dT T T Replacing c by the expression (1 – TC/TH). Equation (9) applies only for ideal We can see that the exergy content of a waste stream can be calculated quite easily in the case of ideal mixtures. we have demonstrated a way to easily calculate the maximum work potential (Ex) one may extract from a given heat resource by using very simple mathematics.COM OCTOBER 2006 . gives: T dEx = C p ⋅ dT ⋅ 1 − 0 T (T 2 − T02 + d ⋅ T 3 − T03 3 ) ( ) (7) (11) Therefore. such as the following: C p = a + bT + cT 2 + dT 3 (13) Values of parameters a. gas Gas Gas Liquid. Thus far. From the definition of the heat capacity at constant pressure. for a constant pressure process and nonreacting flow. the integration of Equation (8) yields: Ex = C p ⋅ (T − T0 ) − T0 ⋅ ln T T0 (12) Some examples (9) With the assumption of constant pressure kept in mind. for reference conditions of 25°C and 1 atm Many commercial process simulators. A more general expression can be derived when the gas pressure is different from the reference pressure [3]: Ex = C p ⋅ (T − T0 ) − T0 ⋅ ln T T0 P + RT0 ⋅ ln P0 For the case where Cp is independent of temperature. we can write the enthalpy differential of an ideal gas as: dH = C p ⋅ dT given by: Ex = ∫ ( dH − T0 ⋅ dS) T0 T = ∫ C p ⋅ dT − T0 ∫ T0 T T Cp T ⋅ dT T0 (8) gases at the same pressure as the reference pressure. simple polynomial relations are often proposed in order to express this temperature dependence. including Aspen Plus.CHE. gas Liquid. °C 150 – 300 150 – 430 150 – 260 100 – 350 80 – 100 90 – 370 150 – 450 Type of effluent Liquid. Equation (9) can be used only if the pressure of the hot effluent is the same as the pressure of the surroundings. tables and diagrams [2] for various working fluids of interest. Figure 1 presents enthalpy and exergy as functions of temperature for nitrogen at ideal state and at a reference pressure. ChemCad. and Prosim Plus. Example 1.
Enthalpy and exergy of steam as a function of temperature. for both saturated steam and hot boiling water. Saturated steam and hot bubbling water: As for the ideal gases above. For instance. at least some recoverable useful work could be produced out of such waste streams. It goes without saying that the total power output of such systems will be lower than the available work potential. we will briefly discuss some technologies available. which in turn.11 for hot bubbling water. the theoretical exergy/enthalpy ratio is close to 0. This means that for a heat resource consisting of 100°C hot stream of nitrogen. even for temperatures as low as 100°C. In the next section. the effect of pressure on the exergy content is insignificant for liquid water. In fact. Alternatives have therefore been proposed. From these three examples. Refrigerants such as R11. Numerous types of apparatus have been proposed for the conversion of lowtemperature heat into useful work using the thermodynamic cycles of heat engines. the exergy of hot water at 80°C and 1 atm is nearly the same as that of hot water at 80°C and saturation pressure. For example. At a temperature of around 100°C. we have shown that it is theoretically possible to use hot gases. Example 3. so that a similar reasoning as the one conducted above can be done to yield an equation similar to Equation (9). the enthalpy and entropy data for steam and bubbling water are wellknown. Enthalpy and exergy of boiling water. such as the organic Rankine cycle (ORC) and the Kalina cycle. The ratio of exergy/enthalpy for nitrogen as function of temperature (T0 = 25°C. for a fluid stream hotter than the environment (T > T0). for the conversion of low grade heat resources to electricity. as well as that of the conversion device itself together with all its components. could be used for producing electricity. enthalpy is defined in quite a similar way as for ideal gases [Equation (6)]. Here one observes that the ratio Ex/H increases with temperature. P at reference level) FIGURE 3. If useful heat cannot be recovered from a hot waste stream for use elsewhere in the plant. The idea behind ORC is the use of working fluids that have a higher vapor pressure than water.Engineering Practice ���� ��������������������������� ������ ��������������������������� ������ ���� ���������������� ������ ������ ������ ������ ������ � � ���������������� ������ ������ ������ ����� ����� ����� ����� � � �� ��� ��� ��� ��� ��������������� ������� �������� ��������� �������� ���� ���� ���� ���� �������������� � �� ��� ��� ��� ��������������� ��� �� ��� ��� ��� ��������������� ��� FIGURE 2. R113. for reference conditions: saturated liquid water at 25°C calculated using Equation (14). Exergy efficiencies as high as 70% are conceivable. It should be noted that. The reference conditions are temperature of 25°C and standard atmospheric pressure. the efficiency of these cycles depends on the nature of the heat source and heat sink. with the reference condition being saturated liquid water at 25°C. The use of the Rankine cycle with steam as working fluid for the production of electricity is wellknown. Incompressible fluids: For incompressible liquids. Ex/H is 0. at 100°C. a maximum of 11% of the total enthalpy is recoverable as shaft work. A more general expression taking into account the pressure effect is: Ex = C ⋅ (T − T0 ) − T0 ⋅ ln T T0 +V ⋅ ( P − P0 ) (15) where C is the specific heat of the liquid and V is the specific volume. Figure 2 shows how the ratio of exergy to enthalpy varies for nitrogen.11.CHE. Example 2.17 for steam and 0. CHEMICAL ENGINEERING WWW. Figures 3 and 4 present enthalpy and calculated exergy respectively for saturated steam and boiling water (saturated liquid water). These two graphs confirm 42 that. for temperatures below 100°C.COM OCTOBER 2006 . higher temperature means higher exergy. Figure 5 shows the evolution of the exergy to enthalpy ratio with respect to temperature. but is not appropriate in the case of lowtemperature (< 240°C) heat sources. low pressure steam or hot water as a source of useful work. for reference conditions: saturated liquid water at 25°C FIGURE 4. We can define an efficiency term for the recovery of exergy: (16) W ηe = ∆Ex net Conversion techniques where Wnet is the net work produced and ΔEx is the exergy variation of a hot stream transferring heat to the system or device (through a heat exchanger). or being developed.
No. Reid. 515–525. Energy. again because it has a much higher vapor pressure compared to water at a given temperature. He is co inventor for two patents and has another patent pending.and masstransport processes.S. ext. This cycle is based on the use of an ammoniawater mixture as a working fluid [9]. pyrolysis and combustion). 11]. ibid. “The Properties of Gases & Liquids. J. and others. A. 110. “Advanced Engineering Thermodynamics. Wall. Phone: 8195391400. Prauznitz J. J. CHEMICAL ENGINEERING WWW. Int. This Grade Heat Sources. No. G9N 7N5. Vol. Exergy Flows in Industrial Processes. Furthermore. thermochemical energyconversion processes (such as gasification. Another interesting thermodynamic cycle strongly considered for utilizing lowtemperature waste heat. 2. the composition of the working fluid can be purposefully modulated to accommodate the available heat resource. 1988. higher exergy efficiency involves moreexpensive design so that a balance should be made between capital cost and operating efficiency. but also for a better ■ environment. in conventional Rankine cycles. Kiari Goni Boulama is a junior scientist working for Institut de Recherche d’HydroQuébec. A hot stack gas. 41. J. Vol. His main area of activities includes process analysis. are promising alternative fluids [6]. 732. 251–253.. D. 3. S. ASHRAE Transactions. Goni Boulama’s scientific interests are heat. Eng. following more closely the temperature decrease of the heat source. No.ireq. conventional steam turbine equipment can be used. Fax: 819 539 1409.. Int.. at LTE laboratory (Laboratoire des Technologies de l’Énergie.. Fax: 8195391409. pp. Bejan A. He is author of several articles published in technical journals and international conference proceedings. Energy. and Flow Exergy of 12 Gases at Low Pressures. and the fact that it is a wetting molecule (it condenses during expansion). Larjola. 8. 2004. Riffat.181–186. and Nguyen. same address as above. 6. and which is on the verge of commercialization. of Ambient Energy. This extra heat expense (vapor superheat) is eliminated when using an ORC with a dry fluid [7]. No. and Poling.CHE. 657.. 1393. He is author or coauthor of more then fifty publications and more than 75 HydroQuébec technical reports. steam is superheated before entering the turbine in order to avoid this problem. 1997. a residual lowpressure steam or even a hot wastewater stream all have the potential to produce some useful work. Province of Quebec. electrosynthesis and electrochemical processes. pp. Shawinigan. Email: goniboulama. Finally. Combined Heat and Power System Driven by Low 7. Another remarkable feature related to the Kalina cycle is that the temperature of the working fluid increases during the boiling process. Vol. ext.ca) a group of the Institut de Recherche d’HydroQuebec (IREQ).Eng.. the LTE being the host institution.. 1452.S. potential can easily be calculated for any kind of stream. Bejan.. 9. For the last 24 years he has been involved as a scientist or project leader in many projects regarding efficient use of electricity in industry and in developing and demonstrating of new processes based on the use of electricity or electrotechnologies. exergy analysis can also be used to improve the efficiency of a process or to pinpoint and quantify imperfections for a given process [10. Vol..E. 4. is the Kalina cycle. 2. 197–208. In the industrial sector. the integration of exergy analysis in the industrial sector contributes not only for better energy efficiency. Edited by Gerald Ondrey Authors Raynald Labrecque is a research scientist working for Institut de Recherche d’HydroQuébec. J... Vol. 1987. less irreversibility is to occur. No. 16. Because of this better match between the temperatures of the two streams. Chapter 5. Email: labrecque. 13. 22. 11. Exergy Flows in Industrial Processes. Energy Conversion and Management. This technology is now mature and well established throughout the world. for reference conditions: saturated liquid water at 25°C R114 have been proposed as ORC working fluids [5]. p. His professional membership includes: Ordre des Ingénieurs du Québec and Association Québécoise pour la Maîtrise de l’Énergie. pp. Absolute Entropy. Vol.M. and M.. degrees in chemical engineering from Laval University (Québec City). HeatActivated DualFunction Absorption Cycle. G. in mechanical engineering from the University of Sherbrooke (Québec). such as isobutene. kiari@lte. Wall. G. Canada. Use of waste heat to make electricity. they are “drying fluids. 1.D. B. Many hydrocarbons. Condensation is highly detrimental to turbine blades and.ireq. Final remarks References 1. 9. One of its interesting features is its flexibility. Waste Heat Recovery of Organic Rankine Cycle Using Dry Fluids. 42.. pp. in energy engineering from the National School of Engineering of Monastir (Tunisia) and a Ph. An advantage of using hydrocarbons is that.���� ��� ���������������� ��������������� ������� ���� ��� ���� ��� ���� � � ��� ��� ��������������� ��� ��������������� ������������ FIGURE 5.” 4th ed. 4. pp. McGrawHill Book Co.C.C. in many cases. Heat and Fluid Flow. The ratio of exergy to enthalpy for steam and boiling water.M. He holds a B. Electricity from Industrial Waste Heat Using Highspeed Organic Rankine Cycle (ORC). pp. 600 De la Montagne Ave. R. 5. isopentane and cyclopentane.COM OCTOBER 2006 43 . 19. 10.ca). and thermodynamic processes for energy conversion. However. p. 2004.B. 2. Int..D. Erickson. since ammonia has a molecular weight close to that of water. 1988. The technology is on the verge of commercialization [8]. 13. 227–235. 539–553. 217–238. Ammonia (R717) has been proposed as an alternative working fluid. 1995. Hung TzuChen. 198. at LET (Laboratoire des Technologies de l’Énergie. 1988. The principal drawback with ammonia is with regard to safety (toxicity). without fuel.” which means that there is no condensation occuring during the expansion process for the production of work. Phone: 819 539 1400. pp. energyefficient electrotechnologies. thermodynamics and energy conversion. He holds B. Vol. Production Economics. 2001. Apart from computing the fraction of the thermal energy that can be converted to motive power. He has been awarded a postdoctoral fellowship by the Natural Sciences and Engineering Research Council of Canada (NSERC). as shown by the examples above.raynald@lte. March.” 2nd ed. Chem. V. a lot of heat is simply discarded into the environment because it is considered as of no value or not useful for a specific process. Blending Geometry with Numerical Computation: Charts for Enthalpy. pp. 1998.
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