Desalination 264 (2010) 84–91

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Advanced energetics of a Multiple Effects Evaporation (MEE) desalination plant

Part I: 2nd principle analysis by a zooming representation at single-effect level
A. Piacentino ⁎, F. Cardona
DREAM — Dpt. Of Energy and Environmental Researches, University of Palermo, Viale delle Scienze, 90128, Palermo, Italy

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

Article history: This paper represents the Part I of a paper in two parts, aimed at proposing a 2nd principle and
Received 9 October 2009 thermoeconomic analysis for a Multiple Effects Evaporation (MEE) process and discussing solutions for
Received in revised form 30 June 2010 optimization and energy saving. After a brief analysis of the thermochemical fundamentals of desalination,
Accepted 2 July 2010
the minimum theoretical work of separation is introduced to represent a reference condition for the
Available online 25 August 2010
assessment of plants' efficiency. A forward feed MEE configuration is then analysed, abandoning the
Keywords:
conventional approach to “at overall plant-level”-analysis; a zooming strategy, based on focusing on the
Desalination physical model of a generic stage (i.e. effect), is preferred to best recognize the margins for systems'
Multiple Effects Evaporation improvement. The energy conversion process taking place in the examined effect reveals very inefficient and
Exergetic efficiency the specific contribute of any subprocess to the overall exergy destruction is evaluated. In the Part II of this
Exergy destruction paper, it will be seen that the cost formation process enables us to perform more accurate optimizations;
Zooming representation also, a realistic approach to energy saving by cost integration will be outlined.
Brine disposal © 2010 Elsevier B.V. All rights reserved.

1. Introduction
Seawater desalination represents an increasingly interesting
solution for the problem of fresh water scarcity. Nowadays several
technologies are available, either thermal (Multi Stage Flash, Multiple
Effects Evaporation, Freezing), mechanical (Reverse Osmosis) or
electrochemical. Most of them easily achieve the 500 ppm Total
Dissolved Solids (TDS) index recommended by the World Health
Organization for drinkable water; the actual bottleneck to make
desalination to represent a viable option for large-scale fresh water
supply is related to the high energetic cost of desalted seawater, which
typically ranges from 4–6 to 50–80 kWh/m3, respectively for mechan-
ical and thermal systems. Significant efforts are thus required to the
scientific community to provide more accurate models and design
criteria, in order to increase the energetic efficiency and thus reduce
the production cost. First law analysis hides the actual margins for
system improvement and is consequently inadequate; 2nd principle-
based approaches, on the contrary, are much more explanatory and
could allow to recognize the origin of the main losses, by introducing
concepts such as the available work (i.e. the exergy). Finally, more
advanced theoretical structures like thermoeconomics could offer a
further contribute to the in-depth understanding of plants' behaviour,
by differentiating the value of resources whose dissipation implies a
same exergy destruction but a different exergetic cost [1].
⁎ Corresponding author. Tel.: +39 091 236302; fax: +39 091 484425.
E-mail address: piacentino@dream.unipa.it (A. Piacentino).
All the above approaches are well consolidated; however, when
applied to the analysis of Thermal Desalination Processes (TDPs),
difficulties and some controversial aspects have to be addressed. Let
us first observe that, differently from most of energy systems, the 2nd
law analysis of TDPs involves simultaneous variations in the
mechanical (i.e. pressure-dependent), thermal (i.e. related to temper-
ature, T) and chemical (related to salts' concentration, Xsalts) fractions
of the exergy associated with feed/desalted/brine flows. Even
descending from Gibbs' studies, the harmonization of 2nd law defi-
nitions for water flows undergoing desalination processes is quite
recent; even higher uncertainty exists as concerns the most reliable
thermoeconomic approach to be adopted. This research work in two
parts is aimed at providing insightful results as concerns the exergetic
efficiency of single subprocesses, offering a rigorous perspective for
thermoeconomic analysis of Multiple Effects Evaporation systems and
investigating the energy saving potential related to process integra-
tion. In its turn, this Part I is structured in two sections: a preliminary
analysis of the thermochemical fundamentals of desalination, and the
description, resolution and interpretation of 1st and 2nd principle
models for a generic stage (i.e. effect) of a MEE system. Focusing the
attention on a single effect has both advantages and drawbacks.
In “modular” systems, where a subprocess repeats quite identically
between a number of components, focusing on a specific module
allows for more detailed analyses than investigating the whole lay-out
as unique; this concept is absolutely intuitive in multi-stage flash
plants, where the number of stages often exceeds 20 or 30: in such
cases it is evidently preferable to perform accurate studies on ther-
modynamic subprocesses at a “single stage level.” While analysing a

0011-9164/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.07.008
 A. Piacentino, F. Cardona / Desalination 264 (2010) 84–91 85

single module, however, we should keep into account that any potential can be expressed as sum [4] of a pure substance chemical
extrapolation of the results obtained at “single module level” to the potential μ*, which may be deducted by tables of properties of pure
“whole system level” introduces some inaccuracy, since the different substances and is related to Gibbs' free energy, and of a function of
modules are characterised by slight differences in the performance. concentration:
In the Part II [2] the potential of thermoeconomics for the

optimization of plant design will be discussed and some aspects μ c = μ c + RT0 ln Xc ½kJ = kmol ð6Þ
related to process integration methods will be investigated in detail.
The two articles are evidently interrelated and reading them as a thus leading to a simplified exergy expression:
whole is preferable.
CH     X
E = ∑c Nc μ c −μ c0 + RT0 ∑c Nc ln c ð7Þ
Xc;0
2. Thermodynamic fundamentals of seawater desalination

where the 1st term on the right hand can be neglected whenever no
The 2nd principle analysis of desalination processes requires the
chemical reactions occur within the solution. The above expressions
use of an extended expression for the Gibbs free energy, accounting
are based on the assumption of ideal solution, defined as a solution for
for the chemical potential of the dissolved species. The generalized
which the partial molar volume and enthalpy of each component
Gibbs Free Energy (FE) expression for simple systems is:
equal the respective volume and enthalpy of the unmixed compo-
CH PH nents (i.e. partial molar volume and enthalpy do not vary across the
FEGibbs = FEGibbs + FEGibbs = H−T0 S−∑c μ c0 Nc ð1Þ
mixing process) [5]. Even for an ideal solution, however, the entropy
of components varies along the mixing process as follows:
where Nc represents the number of moles of the c-th specie, μ c0 its
chemical potential in equilibrium with the environment and T0 the ideal mixt: pure
sc ðT; pc Þ = sc ðT; pÞ−R ln Xc ð8Þ
reference environment temperature. The last term, not included in the
expressions usually adopted in energy systems' analysis, accounts for
where, being Xc b 1, it is evident that entropy is generated and that any
the variations, always occurring in TDPs, of the chemical composition
spontaneous mixing process is intrinsically non-reversible. In Eq. (8),
of solutions. Eq. (1) can be alternatively formulated in specific terms.
obtained for a mixture of ideal gases fulfilling Dalton's law, pc and p
Being exergy a co-property of the water and the surrounding envi-
represent the partial pressure of the c-th component and the total
ronment thermodynamic states, in order to pass from the free energy
pressure of the solution, respectively, being pc equal to Xcp. Eq. (8),
to the exergy expression we have to define a reference environment.
however, is also valid for liquid solutions where the concentration of a
With reference to the usual approach, based on the following defi-
component maintains sufficiently low, as occurs in seawater desali-
nition of a dead state:
nation plants. The specific exergy of salty water can be expressed as
h i sum of three contributes:
h0;dead −To s0;dead = ∑c μ c0 Xc ð2Þ
T0 ;p0;fXc0 g
tot CH T P
Δe = Δe + Δe + Δe ð9Þ
an alternative approach was suggested by El-Sayed [3], based on an
intermediate dead state, with the same p0 and T0 but a chemical where the chemical exergy has been already attained in Eq. (7) and
potential μi coincident with the chemical potential of the solution at the thermal and mechanical fractions of exergy are calculated by:
its actual composition:  
T T P p−p0
Δe = cp ⋅ T−T0 −T0 ln Δe ≈ ð10:a; bÞ
½h0 −To s0 T0 ;p0;fXc g = ∑c μ c Xc ð3Þ T0 ρsolution

Basing on Eq. (3), in fact, the specific exergy may be expressed as: Another concept related to exergy is the theoretical (minimum)
work of separation of seawater into a low salinity distillate/permeate
e = ðh−h0 Þ−T0 ðs−s0 Þ + ∑c ðμ c −μ c0 ÞXc ð4Þ and a high salinity brine. In order to obtain its analytical expression,
let us consider the spontaneous mixing of two species, A and B,
When the exergy associated with other material streams (com- constituting a solution. The entropy balance of a steady and adiabatic
bustion gases, other fluids, etc.) has to be also computed, the use of mixing process of two species is:
two distinct dead states can be convenient [3]. Let us indicate with the
sinput −soutput + sgen = 0 ð11Þ
subscript “r” the dead state adopted for the salty water (all the
dissolved species being included in a set {c1}) and with the subscript
where Eq. (8) suggests the correct expression to calculate entropy
“0” the dead state for any other specie (included in a set {c2}); we may
generation:
write:
sgen = −R∑c Xc lnXc ð12Þ
∑c ðμ c −μ c0 ÞXc = ∑c1 ðμ c −μ cr ÞXc + ∑c1 ðμ cr −μ c0 ÞXc ð5Þ
+ ∑c2 ðμ c −μ c0 ÞXc The exergy destruction associated with the mixing process can be
calculated by the Gouy–Stodola theorem:
In Eq. (5) the 2nd term on the right hand is a constant of no
interest: adopting a conventional dead state (for instance, air at edest = To sgen = −RT0 ∑c Xc ln Xc ð13Þ
T0 = 20 °C, p0 = 101.3 kPa) for the salty water would have implied
working with high and useless values of the chemical exergy, being This exergy destruction is evidently related to irreversibility; as the
the deviations computed from a non-representative reference spontaneous mixing of two species A and B into a solution does not
condition. generate any useful work, once indicated with wrev the theoretical
Although the problem seems clearly formulated, the evaluation (i.e. maximum) work that could have been produced by a reversible
of chemical potentials should be briefly discussed. Classical thermo- mixing process, we get:
chemistry suggests us to express them as functions of activity coef-
ficients or fugacities of the dissolved species; however, the chemical wrev −edest = 0 ð14Þ
86 A. Piacentino, F. Cardona / Desalination 264 (2010) 84–91

Due to the definition of reversible transformation, wrev represents, and a maximum for r≅1:
at the meantime, the minimum theoretical work needed to separate
!
the two species from the solution. Particularizing Eq. (13) with ðr≅0Þ ⋅ feed ⋅ Xsalts;0
respect to the assumption of two only species A and B, being XA + W m in;partialsep: = − Nprod RT0 lnXsalts;0 + ln Xwater;0 ð19Þ
Xwater;0
XB = 1, we get:

Obviously, the pre-treatment costs follow an inverse trend (i.e.

wmin = −RT0 ½XA lnXA + ð1−XA Þ ln ð1−XA Þ ð15Þ
decrease with r) and the existence of a trade-off can be expected. The
molar concentration of salts should include the effects of ionic
Eq. (15), however, does not provide an actual feasible target for an dissociation; for seawater, in particular, we introduce a dissociation
optimization process oriented to minimize the specific work con- factor φ = 2, because of the complete dissociation of NaCl into Na+
sumed per m3 fresh water. In real world applications, in fact, complete and Cl− ions.
separation of salts from seawater is never pursued; we rather attempt This brief resume of the 2nd principle fundamentals of desalination
to separate a low salinity distillate/permeate from a concentrated was given to provide solid bases to the study proposed ahead in the
brine to be disposed. We have thus to move towards the definition of a paper. Let us now discuss about the sign of the exergy flows associated
theoretical work of partial separation; the conceptual approach to with the brine disposed. The mechanical exergy content of a system,
determine it is shown in Fig. 1 [5]. A desalination plant covers only a associated with a pressure disequilibrium with the environment, is
fraction of the total separation process, generating two outputs, the always positive [6]; depending on whether p b p0 or p N p0, the re-
brine and the fresh water, whose theoretical work of separation is still versible work toward equilibrium will be made by the environment on
non null. the system or vice versa but, in any case, some surplus technical work
With reference to the notation in Fig. 1, the partial separation work could be extracted. Something similar can be said about chemical
is determined by: exergy: both above and below the dead state concentration Xfeed, salty
water has some work extraction potential, as suggested in [3]. This
⋅ ⋅ ⋅ ⋅
feed feed prod B can be easily proven by an ideal exercise: if we use a semi-permeable
W min;partial sep: =Wmin;total sep: − W min;total sep: − W min;total sep: ð16Þ
membrane to separate seawater from a salty water at any X ≠ Xfeed, we
will get a geodetic prevalence both when X N Xfeed and X b Xfeed. Pilot
The following expression is determined for the partial separation applications of systems producing electricity by Pressure-Retarded
⋅
of a molar flow rate Nfeed (in mol/s): Osmosis (PRO) have been proposed, which exploit the ΔX between
fresh and salty water in proximity of rivers' estuaries [6]; in order to
!
⋅
feed
½ ⋅
W min;partialsep: = −RT0 NB Xsalts;B ln
Xsalts;B
Xsalts;0
+ Xwater;B ln
Xwater;B
Xwater;0
!
address rigorously the topic, however, we should relate brine
concentration with processable (and not “thermodynamic”) exergy
[7], i.e. with the part of chemical exergy which could be converted into
⋅
+ N prod Xsalts;prod ln
Xsalts;prod
Xsalts;0
+ Xwater;prod ln
Xwater;prod
Xwater;0  electricity by economically convenient and technically viable processes.
Basing on the water transport equation:
ð17Þ
⋅
M = Δπ⋅Kw ⋅Amembrane ð20Þ
We usually define a recovery ratio r of desalination units, rep-
resenting the amount of product per unit mass of feed water. The a minimum 5 W/m2 economical power generation rate has been
expressions of the theoretical work of separation described above have estimated [7]. The term Δπ is approximately calculated by Van't Hoff
⋅
feed
general validity for any r, but the Wmin;partialsep: varies with r, finding a law as 75.8 kPa per 1000 ppm TDS, thus resulting for a ΔX = 35,000 ppm
minimum for r ≅ 0 (where Xsalts,B ≅ Xsalts,0, Xwater,B ≅ Xwater,0): (typical concentration gradient between seawater and a 70,000–
80,000 ppm brine) a 24–28 bar differential pressure, that is equivalent
⋅ feed ⋅ ⋅ to a 200–250 m water head in a hydropower plant. Thin-Film Composite
ðr≅0Þ
W m in;partialsep: = − Nprod RT0 lnXwater;0 ≅ Nprod RT0 Xsalts;0 ð18Þ (TFC) membranes are close to the economic viability for PRO power

Fig. 1. Conceptual scheme for the determination of the theoretical work of partial separation.
 A. Piacentino, F. Cardona / Desalination 264 (2010) 84–91
production; for this reason, in the following of this study (in particular in
the Part II of the paper) the brine disposed will be considered an
unexploited but valuable resource, assigned with a non-null exergetic
cost.
3. Thermodynamic model of the Multiple Effects
Evaporation system
In this section a Multiple Effects Evaporation (MEE) system is
examined, which represents the largely most diffuse scheme of
thermal desalination plants for medium to low fresh water production
rates [8]. Among the possible alternatives, a forward feed lay-out is
considered, schematically presented in Fig. 2; in such systems the
brine and the distillate pass through successive effects in the direction
of decreasing pressures and temperatures, while the feed water flow
is pre-heated in the opposite direction (from the last to the 1st effect).
The operation of the system can be described as follows. An Mcw + Mf
flow rate is introduced at the condenser through intake seawater
facilities; here this mass flow subtracts the surplus heat from the n-th
(i.e. last) effect, a fraction being wasted by discarding the cooling
water flow rate Mcw and the rest representing the feed, admitted to
the line of preheaters. Passing through the series of preheaters (one
for each effect but for the first and the last), this feed flow Mf recovers
some latent heat released from two small distillate flow rates deriving
by two flash expansions, as will be cleared later. The pre-heated water
enters the 1st effect where the latent heat released by the condensing
feed steam is used to separate a D1 distillate flow rate; a B1 flow rate of
concentrated brine falls down the evaporator tubes. Both the distillate
and the brine pass to the 2nd effect, whose operating pressure and
temperature are lower by Δp and ΔT; here a further distillate flow rate
D2 is separated from the inlet brine B1 by the condensing distillate
vapour D1 formed in the 1st effect. A lower brine flow rate B2 falls
down the evaporator tubes, with a higher XB2 concentration. The
process repeats identically up to the (n − 1)-th effect, because, as said
above, the last effect is integrated with a condenser for the discharge
of surplus heat.
In order to properly model the system, mass balances for water
and salts, energy balances and heat transfer equations must be
written. Mass balances of the solution for the 1st and for a generic
effect are written as follows:
B1 = Mf −D1 Bi = Bi−1 −Di ð21:a; bÞ
Fig. 2. Simplified scheme of a forward feed MEE plant.
87
while the analogue mass balances for salts are:
Mf Bi−1
X1 = Xf ⋅ Xi = Xi−1 ⋅ ð22:a; bÞ
B1 Bi
The thermal load Q (heat rate exchanged at the evaporator) of a
generic effect, expressed in kW, is:
Q i = Di λvi = Di−1 λvi−1 ð23Þ
Eq. (23) suggests us that, assuming an adiabatic process, the
distillate production rate slightly decreases from the 1st to the last
effect due to the increase in the latent heat of vaporization λ at lower
temperatures. From a heat transfer viewpoint, the thermal load can be
expressed by:
Q i = Ai Ui ΔTi ð24Þ
where UiΔTi is constant for all the effects, being Qi and Ai constant.
Eqs. (21)–(24) are sufficient to solve the problem, finding the overall
heat transfer area, the feed steam flow rate and, for each effect, the brine
and distillate flow rates and the brine concentration. After having fixed
the salinity of the feed and its temperature at the exit of the condenser,
the ΔTtotal along the n effects and the desired concentration of the
rejected brine, the solutions are easily found by an iterative approach.
Coherently with the declared goal of this paper, aiming at offering
a clear understanding of the contributes of each specific irreversibility
to the overall exergy balance, we will focus the attention on a generic
i-th effect and examine a more refined model of the process [9], that is
schematized in Fig. 3.
With respect to the simplified scheme, two more fluxes d′i and d″i
of distilled vapour are obtained by flash, according to the two
following processes:
- The amount d'i is generated due to the flash of the brine flow Bi − 1,
generated at the (i − 1)-th effect, when admitted to the i-th effect
characterised by a lower pressure. The energy balance for this
process, assumed as adiabatic, gives:
0
0  0 TB;i−1 −Ti
di = Bi1 −di ⋅cp ⋅ 0 ð25Þ
λvj
where T'i differs from the boiling temperature Ti of the i-th effect by
the Non Equilibrium Allowance NEA'i, that is the deviation in the
88 A. Piacentino, F. Cardona / Desalination 264 (2010) 84–91

Fig. 3. Accurate model of the i-th effect of a MEE desalination plant.

temperature achieved by flash expansion due to several factors, 4. Exergetic analysis of a case study
such as the higher energy content entrapped in the brine (and not
available for vapour formation), the thermodynamic irreversibility A detailed exergetic analysis is proposed for the 3rd effect of a 6
and the hydraulic overpressure below the brine surface. In the effects MEE plant; a case study partially solved in [9] is used as a
present work the NEA will be calculated by the expressions reference example. It refers to the following boundary conditions:
proposed in [9];
a. Feed steam temperature: Ts = 100 °C;
- The amount d''i is generated by the flash expansion of the b. Seawater salinity: Xf = 42,000 ppm;
condensed distillate Di − 1 at the inlet of the flashing box, i.e. the c. Salinity of rejected brine: X6 = 70,000 ppm;
component where it mixes with the distillate produced in the d. Feed water temperature: Tf = 35 °C;
previous effects at a pressure lower than the saturation pressure at e. Seawater temperature: Tcw = 25 °C.
Tci. The energy balance for this process is expressed as:
The simulated values, obtained in [9] basing on the simplified
 00

00  00  Tci1 −Ti model, were assumed as “approximately correct” (representing just a
di = Di−1 −di ⋅Cp 00 ð26Þ preliminary solution) also for the refined physical model presented in
λvi Fig. 3, in order to avoid solving by complex modified fixed point
iteration methods the whole lay-out. Starting from this preliminary
Eq. (26) allows us to calculate the distillate flow rate when we solution, the results were locally (i.e. just for the i-th effect) adjusted
know the temperature T''i , related to Tvi'' by: to account for the two flash phenomena described in Section 3. This
approach is not rigorous, but the obtained values will not differ
00 00 00
substantially from the exact ones, due to the negligible role played by
Ti = Tv + NEAi ð27Þ the flash-derived flows d'i and d''i . The results are presented in Table 1.
i
The following aspects can be remarked:

In Fig. 3 feed pre-heating is achieved by condensing the fluxes d′i e - Mechanical exergy always assumes negligible values and can be
d″i. This accurate thermodynamic model will be used in the next thus excluded from our analysis;
sections and in the Part II of this paper to perform energetic and - Chemical exergy always assumes small values, with respect to
thermoeconomic analyses. thermal exergy. However, being it included in the productive

Table 1
Results of the detailed physical model for the 3rd effect of a 6 effects MEE plant.
⋅ T ⋅ CH ⋅ tot
t [°C] p [kPa] X [ppm] m⋅ [kg/s] eT [kJ/kg] ep [kJ/kg] eCH [kJ/kg] etot [kJ/kg] E [kW] E [kW] E [kW]

Bi.1 84.96 57.81 48,611 2.1606 24.897 −0.043 0.048 24.902 53.79 0.104 53.803
Di − 1,vap 83.30 53.67 18 0.1693 431.555 −0.047 3.5934 435.10 73.06 0.608 73.662
Di − 1,cond 83.10 53.26 18 0.1693 23.576 −0.048 3.5934 27.121 3.991 0.608 4.591
Mf-inlet 47.09 72.10 42,000 2.5 4.643 −0.029 0 4.614 11.61 0 11.61
Mf-outlet. 53.21 72.04 42,000 2.5 6.849 −0.029 0 6.820 17.12 0 17.12
d'i 78.21 42.27 22 0.0234 405.11 −0.059 3.5932 408.64 9.479 0.084 9.562
d''i 76.84 42.27 18 0.0019 394.778 −0.059 3.5934 398.31 0.765 0.007 0.757
d'i+ d''i 76.60 42.15 22 0.0253 19.211 −0.059 3.5932 22.745 0.484 0.091 0.575
Bi 76.84 42.27 52,704 1.9922 19.365 −0.059 0.116 19.422 38.58 0.231 38.692
Di 76.15 42.27 18 0.1677 392.192 −0.059 3.5934 395.73 65.77 0.603 66.363
 A. Piacentino, F. Cardona / Desalination 264 (2010) 84–91 89

purpose of the system, it cannot be excluded from a thermo- d. Heat exchange at the pre-heater
economic analysis. The condensation latent heat is released to pre-heat the feed
water; the exergy destruction associated with the heat transfer
Much more interesting results will emerge from detailed exergy across a finite ΔT is calculated by:
balances for the specific subprocesses, which are plotted (out of scale,
⋅ ⋅ ⋅ ⋅ ⋅
for clarity of representation) in Fig. 4. pre−heating
E destr
T T
= E d0 + E d00 + E Mf −inlet − E d0
T T
00 ð33Þ
i i i
+ di ;cond
⋅
a. Flash at brine inlet T
− E Mf −outlet = 5:718 kW
Being d'i ≪ Bi − 1, the thermal exergy destruction could be
approximately calculated by:
  The results of the analysis are also presented in Table 2, for a more
⋅
T T 0 T −T0
Δ E ≅ Bi−1 cp TBi−1 −T3 −T0 ln B−1 −di λ3 3 ð28Þ immediate comparison; the large prevalence of the exergy destruc-
T3 T3
tion due to heat exchange at the evaporator and the pre-heater is
evident. The last column in Table 2 presents the share of the overall
exergy destruction associated with each process; in [2] it will be
Alternatively, referring to the exact values presented in Table 1 we
shown that these values are very sensitive to the ΔT between two
can easily get:
consecutive effects.
⋅ ⋅ ⋅ ⋅ ⋅
inlet flash T CH AF;T AF;CH
E destr = E Bi −1 + E Bi−1 − E ðB −1Þ−d0 − E ðB −1Þ−d0 ð29Þ 5. Interpretation of results
i i i i

⋅ ⋅
T
− E d0 − E d0 = 0:817 kW
CH According to the most common approach, the subprocesses should
i i
be ordered basing on their exergy destruction, i.e. their specific
contribute to the overall system inefficiency. We would consequently
recognize that the heat exchange at the evaporator is the irreversible
In order to calculate all the terms in Eq. (29), the intermediate
process with the highest entropy generation; assuming that ΔT should
state AF (i.e. After Flash) of the brine had to be evaluated. The
be reduced as much as possible is the wrong conclusion we would
concentration resulted:
immediately achieve. While contributing to reduce the exergy
Bi−1 destruction at the evaporator, in fact, a decrease in the ΔT could
AF
XB = XBi−1 ⋅ 0 = 49; 143 ppm ð30Þ eventually induce increases in the exergy destruction rate related to
Bi−1 −di
the other three main sources of irreversibility. Also, from the analysis
proposed in Section 4, reducing the ΔT at the pre-heater would
emerge as a priority for an efficient design.
b Heat exchange at the evaporator The above approach is evidently misleading, because of some main
In the hypothesis of adiabatic process, the exergy destruction due reasons:
to heat exchange across a finite ΔT results:
1. What is actually important is not the exergy destruction, but the
!
⋅
evap 1 1 associated cost. Theoretical analyses of energy systems [1] have
E dest = D3 λv3 ⋅ − ⋅T0 = 7:71 kW ð31Þ clearly shown that small exergy destructions might induce either
T3 TDi−1
small or large destruction of resources, depending on the value of
the resources consumed;
c. Flash at the flashing box
2. An improvement of the system requires recognizing all the effects
In the flashing box the distillate Di − 1,cond partially flashes due to
of a marginal variation in a design variable; such effects usually
the lower pressure in the box. The amount of thermal exergy
propagate throughout the system, being this propagation hardly
destroyed (pressure-dependent exergy variations are neglected)
predictable if not investigated by appropriate techniques as those
can be calculated as follows:
provided by thermoeconomics;
⋅
flashingbox
⋅
T
⋅
T
⋅
T
3. We have lost any relation with the actual target, represented by the
E destr = E Di−1;cond − E ðD Þ−di − E di = 3:991−3:216
00 00 ð32Þ theoretical work of separation introduced in Section 2. The exergy
i−1;cond

balances (Eqs. (29), (31)–(33)) do not include the productive

−0:765 = 0:01 kW
purpose of the subprocesses, being neither possible to define their
exergetic efficiencies nor to use them as a more reliable figure of
merit for ordering the subprocesses. Not all the “exiting exergy
flows” in Eqs. (29), (31)–(33) will represent “useful flows”; the
thermal exergy of the brine, for instance, will be partially used to
produce further distillate in the successive effects, the rest being
destroyed at the condenser where the surplus heat is dissipated. In
order to properly evaluate the exergetic efficiency of each

Table 2
Results of the exergy analysis performed for the examined 3rd effect.

Exergy destruction [kW] Exergy destruction

[% of the overall
exergy destruction]

Flash at brine inlet 0.817 5.73 %

Heat exchange at the evaporator 7.710 54.09 %
Flash at the flashing box 0.01 0.07 %
Heat exchange at the pre-heater 5.718 40.11 %
Fig. 4. Schematic of the subprocesses occurring in the examined 3rd effect.
90 A. Piacentino, F. Cardona / Desalination 264 (2010) 84–91

subprocess, we should focus our attention on its productive neglecting the flash phenomena, an unfeasible ΔT below 1 °C should
purpose, i.e. on the expected “useful product” of the specific be imposed at the evaporator.
subprocess. The very low efficiency obtained is coherent with the common
practice, where MEE plants are rarely fuelled by conventional
As concerns the last item, let us consider the minimum theoretical
combustibles, except in Middle-East countries; they might represent
work of separation; which is its best expression, with reference to the
a rational technology where low temperature surplus heat should be
examined 3rd effect of a 6 effects MEE plant? The 3rd effect receives a
discarded by productive processes [10]. In such cases, however, the
feed represented by the brine discarded from the 2nd effect; it is
system must be optimized to maximize the Performance Ratio (PR,
intuitive that Eq. (17) can be here applied assuming a reference
ratio between the flow rates of distillate and feed steam) or to
condition represented by the state of Bi − 1:
minimize the cost per m3; in order to achieve such results and to
! overcome the limits discussed in the items 1 and 2 of the numbered
⋅ B
Wmin;partialsep:
i1
½ ⋅
= −RT0 NBi Xsalts;Bi ln
Xsalts;Bi
Xsalts;Bi−1
+ Xwater;Bi ln
Xwater;Bi
Xwater;Bi−1
+ list at the beginning of this section, thermoeconomic modelling
could play a primary role. In the Part II of this paper a detailed

ð
⋅
Xsalts;ðD + di Þ
0 thermoeconomic analysis will be proposed, capable to reflect the
i
+ Nprod Xsalts;ðDi + di 0 Þ ln ð34Þ mutual interactions among exergy and fluid flows.
Xsalts;Bi−1

Þ
Xwater;ðD 0
+ di Þ
6. Conclusions
i
+ Xwater;ðD 0
+ di Þ
ln = 806:6 W
i Xwater;Bi1
The proposed analysis revealed that Multiple Effects Evaporation
⋅ ⋅ ⋅ ⋅ CH plants are intrinsically inefficient systems for seawater desalination.
Eq. (34) provides a value very close to “E CH
Bi + E CH
Di + 0 − EB
E CH ,” After having pointed out that brine disposal is associated with an
di i−1

as expected. In fact, the productive purpose of the stage is “obtaining actual (although often negligible) exergy lost, an innovative approach
a departure of salts concentration from the equilibrium with the based on a 2nd principle analysis and a zoomed representation of a
environment for the distillate flow rate “Di + d'i””; this assumption is single stage (i.e. effect) allowed us to identify the specific contributes
consistent with the productive purpose of the whole plant, that is of any subprocess to the overall exergy destruction. These results
“obtaining a departure of salts concentration from the equilibrium represent preliminary instruments for the advanced energetic
n  0

with the environment for the distillate flow rate ∑ Di + di .” Also, analyses that will be presented in the Part II of this paper, where
i=1 the potential of thermoeconomics for design optimization and the
the possibility to consider “ECH CH
Bi − EBi − 1 ” as an additional product has margins for energy saving by process integration will be assessed.
been discussed at the end of Section 2. Actually, assimilating the 3rd
effect to a black box, the chemical exergy of the distillate (and the Nomenclature
brine, if used) is not the only useful output; in fact, pre-heating of the A Heat exchange area [m2]
feed represents another positive result and should therefore be taken B Brine
into account when calculating an overall conversion efficiency: cp Specific heat [kJ/kg °C]
  D Distillate by evaporation
ECH CH CH CH T
Bi −EBi−1 + EDi + Ed0 + EMf−outlet −EMf−inlet
T
d Distillate by flash
3rd effect
ηex;I type =  i   ð35Þ ⋅
e, E Specific exergy [kJ/kg] and exergy flow [kW]
ETDi−1 ;vap −ETDi−1;cond −ETDi + ETB −1 −ETBi
i FEGibbs Gibbs Free Energy
h Specific enthalpy [kJ/kg]
6:414
= = 0:346 Kw Water permeability [m3/s m2 kPa]
18:509
Mf Feed flow rate [kg/s]
⋅
rd N, N Number of moles and moles flow rate
If pre-heating was not included, an η3ex,Ieffect
type ≅ 0.05 would have
NEA Non-Equilibrium Allowance
been obtained; hence, pre-heating apparently represents an unavoid-
p pressure
able practice to make MEE desalination viable. It was said “apparent- ⋅
Q Heat rate transferred [kW]
ly” because the above statement results from an analysis at single-
R Universal constant of gases
effect level; considering the whole plant, the thermal balance of the
r Recovery ratio, dimensionless
condenser might significantly affect the total thermal exergy balance,
s Specific entropy [kJ/kg K]
being a large amount of surplus exergy wasted. The exergetic
T Temperature [°C, K]
efficiency presented in Eq. (35) is indicated as “I type”; it includes
TDP Thermal desalination process
the productive purpose of the system, differently from the exergetic ⋅
w, W Specific work [kJ/kg], power [kW]
efficiency “II type” which does not include it:
X Concentration
∑Ej ∑Ei
i∈finletsg
ηex;I type = j∈fuseful outputsg
ηex;II type = ∑Eo ð36:a; bÞ Greek letters
∑Em
m∈fresources consumedg o∈foutletsg φ Ionic dissociation factor
λ Latent heat of vaporization
μ Chemical potential
I type indicators are much more explanatory than II type ones,
ηex Exergetic efficiency
especially for desalination systems. While the thermal exergy of the
π Osmotic pressure
brine is an addictive term at numerator in Eq. (36.b), it becomes a
ρ Density
subtractive term at the denominator in Eq. (36.a); this last approach is
more correct, because EBiT represents, for the i-th effect, a “non
converted exergy flow,” that is left available to successive effects. The Superscripts
above analysis suggests us that converting thermal exergy into AF After Flash at brine inlet
chemical exergy by distillation is intrinsically inefficient; this fact can CH Chemical
be proven by observing that in order to achieve a 0.8 efficiency, even PH Physical
 A. Piacentino, F. Cardona / Desalination 264 (2010) 84–91 91

p Mechanical, i.e. related to pressure [4] G. Wall and M. Gong, On exergetics, economics and desalination, in DESWARE-
Encyclopedia of Desalination and Water Resources, EOLSS Publishers,Oxford, ISBN
T Thermal 09534 9442 X, free access online at the website: www.desware.net.
[5] Y. Cerci, Y. Cengel, B. Wood, N. Kahraman, E.S. Karakas, Improving the
thermodynamic and economic efficiencies of desalination plants: minimum
Subscripts work required for desalination and case studies of four working plants,
Desalination and Water Purification Research and Development Program, Final
destr Destruction
Report N. 78, Agreement No. 99-FC-81-0183, 2003.
f Feed [6] K. Gerstandt, K.V. Peinemann, S.E. Skilhagen, T. Thorsen, T. Holt, Membrane
s Feed steam processes in energy supply for an osmotic power plant, Desalination 224 (2008)
0 State of reference environment 64–70.
[7] A. Valero, J. Guallar, On processable exergy: a rigorous approach, in: Analysis of
Thermal and Energy Systems, ed. D.A. Kouremenos, G. Tsatsaronis, C.D.
Rakopoulos, Athens, Greece: University of Athens, 1991.
[8] A.S. Nafey, H.E.S. Fath, A.A. Mabrouk, Thermo-economic investigation of multi
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