Modeling and Simulation of Saline Extractive Distillation Columns For The Production of Absolute Ethanol

Computers and Chemical Engineering 27 (2003) 527 /549
www.elsevier.com/locate/compchemeng
Modeling and simulation of saline extractive distillation columns for

the production of absolute ethanol
Mario Llano-Restrepo *, Jaime Aguilar-Arias
School of Chemical Engineering, Universidad del Valle, Apartado 25360, Cali, Colombia
Received 1 March 2002; received in revised form 27 September 2002; accepted 30 September 2002
Abstract
A steady-state equilibrium-stage model based on normalized MESH equations is proposed to simulate saline extractive
distillation columns and applied to the production of absolute ethanol, using CaCl2 to break the ethanol /water azeotrope. Among
the activity coefficient models available for mixed solvent/salt systems, the NRTL-E model (with refitted parameters), is shown to be
the most accurate to correlate the experimental vapor /liquid equilibrium (VLE) data available for the ethanol/water/CaCl2 system.
A model is proposed and implemented to calculate the salt contribution to the liquid phase enthalpy by combining calorimetric
quantities of the solute such as its relative apparent enthalpy and the infinite dilution values of its integral heat of solution and
partial isobaric heat capacity. The column model is solved by use of the Newton /Raphson method with a damping factor found by
minimizing the Euclidean norm of the vector of discrepancy functions associated with the MESH equations.
# 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Modeling; Simulation; Extractive distillation; Salt effect; Absolute alcohol; Anhydrous ethanol
1. Introduction registered by Adolf Gorhan in the period 1932/1934

(Gorhan, 1932a,b, 1933, 1934), which were the basis for
Extractive distillation by use of a dissolved salt as the implementation of the HIAG process (described in
separating agent, instead of a liquid solvent, is a detail in International Sugar Journal, 1933), licensed by
relatively neglected unit operation that can be applied DEGUSSA in Germany (Furter, 1972, 1992). According
to some systems for which relatively small concentra- to Furter, over 100 plants, with production capacities of
tions of salt are capable of increasing considerably the up to 43 kt/year, based on that process, were built
relative volatility of the more volatile component of the between 1930 and 1950 in Europe and elsewhere for the
solvent mixture to be distilled. This behavior, known as production of absolute ethanol (that was blended with
salt effect, is due to the preferential solvation of the ions gasoline to make gasohol containing 10% ethanol).
(formed when the salt dissociates in solution) by the less Furter also related that the last of those plants ceased
volatile component of the solvent mixture. In such a operation in 1965, in Brazil. The HIAG process
case, it is said that the more volatile component is salted employed a 70/30 molten mixture of potassium and
out from the liquid to the vapor phase. Use of salts to sodium acetate (fed into the hot reflux stream of the
break the ethanol /water azeotrope for industrial pro- distillation column) as agent to break the azeotrope, and
duction of absolute (i.e. water-free or anhydrous) produced 99.8%/ ethanol (i.e. absolute alcohol). Users
ethanol from dilute mixtures dates back to the patents of the HIAG process claimed lower capital and operat-
ing costs (energy consumption) in comparison with
conventional azeotropic distillation using benzene or
* Corresponding author. Tel.: /57-2-331-2935; fax: /57-2-339-
2335.
extractive distillation using ethylene glycol (Interna-
E-mail address: mllano@mafalda.univalle.edu.co (M. Llano- tional Sugar Journal, 1933; Furter, 1972, 1992). Con-
Restrepo). sidering such documented benefits, it is quite surprising
0098-1354/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 9 8 - 1 3 5 4 ( 0 2 ) 0 0 2 1 5 - 6
528 M. Llano-Restrepo, J. Aguilar-Arias / Computers and Chemical Engineering 27 (2003) 527 /549
Nomenclature
C number of components in the system
Ei,j equilibrium relationship discrepancy function for component i at stage j
fj generic discrepancy function for stage j
F vector of discrepancy functions
Fj total feed-stream flow rate entering stage j
hL,j molar enthalpy of liquid stream leaving stage j
hV,j molar enthalpy of vapor stream leaving stage j
hF,j molar enthalpy of feed stream entering stage j
Hj energy balance discrepancy function at stage j
J Jacobian matrix
Ki,j VLE ratio
L1 iterated reflux flow rate
L1 specified reflux flow rate
LN iterated bottom product flow rate
LN specified bottom product flow rate
Lj liquid flow rate leaving stage j
Mj overall material balance discrepancy function at stage j
Mi,j material balance discrepancy function for component i at stage j
N number of equilibrium stages
N number of iterated variables (or discrepancy functions)
P column pressure
Psat
i,j vapor pressure of component i at stage j
Qj heat load to stage j
R universal gas constant
S1 specification constraint for a total condenser
SN specification constraint for a partial reboiler
Sj stoichiometric constraint discrepancy function at stage j
T damping factor in the modified Newton /Raphson method
Tj temperature at stage j
Uj liquid side-stream flow rate at stage j
Vj vapor flow rate leaving stage j
vsat
i ,j saturated liquid molar volume of component i at stage j
Wj vapor side-stream flow rate at stage j
X vector of iterated variables
xi,j liquid phase mole fraction of component i at stage j
yi,j vapor phase mole fraction of component i at stage j
zi,j feed-stream mole fraction of component i at stage j
x1? liquid phase mole fraction of ethanol on a salt-free basis
Greek symbols
gi,j activity coefficient of component i at stage j
o step size for numerical perturbation method
/8̂ / partial fugacity coefficient of component i at stage j
i;j
8sat
i ,j fugacity coefficient of pure component i at saturation at stage j
that the HIAG process appears to be a neglected choice Cook and Furter (1968), demonstrating that elimination
for the industrial production of absolute ethanol at the of the ethanol/water azeotrope was feasible at relatively
present time. small concentrations of the agent. Moreover, those
A pilot plant study of the extractive distillation authors made a comparison of benefits and disadvan-
process with potassium acetate as separating agent, tages between dissolved salts and conventional liquid
using a bubble-cap tray column, was carried out by separating agents, which turned out to be highly
M. Llano-Restrepo, J. Aguilar-Arias / Computers and Chemical Engineering 27 (2003) 527 /549 529
favorable to the use of salts. Cook and Furter also diethyl ether) and extractive distillation (using ethylene
proposed and experimentally implemented an ingenious glycol or gasoline) processes and also with two non-
solution to the problems associated with the feeding and distillation processes (solvent extraction and membrane
dissolving of the salt into the reflux stream of the pervaporation). It was found that extractive distillation
distillation column. Some time later, Schmitt and using CaCl2 has a lower energy requirement as com-
Vogelpohl (1983) demonstrated the feasibility of the pared with all the conventional alternatives (and solvent
elimination of the ethanol /water azeotrope using po- extraction, as well) and almost the same consumption as
tassium acetate for a continuous pilot-plant sieve-plate membrane pervaporation (which, at present, is widely
column, and studied the effect of salt concentration and used to produce ethanol for gasohol in some of the
reflux ratio on the operation of the column. northcentral corn-producing states of the US). Barba et
An attempt to simulate the saline extractive distilla- al. (1985) also made a theoretical evaluation of the
tion of ethanol/water mixtures was made by Siklós, dehydration process using CaCl2, by simulating a
Timár, Ország, and Ratkovics (1982). Two salts at mathematical model of the column about which they
saturation were tested as separating agents: sodium only reported the formal matrix structure of the
chloride and potassium acetate. For the calculation of equations and the numerical values of the parameters
vapor/liquid equilibrium (VLE), the salt-containing required for an activity coefficient model of their own
liquid mixture was treated as a pseudo-binary system, that they described elsewhere. No details were provided
and either the Wilson equation or an empirical correla- in their paper on how the enthalpies of the liquid and
tion was used for estimating the equilibrium ratios of the vapor streams were calculated. As can be inferred from
pseudo-components ethanol and water. A simultaneous Fig. 1 in their paper, the set of experimental VLE data
correction procedure based on the Newton /Raphson for the ethanol/water/CaCl2 system at 1 atm, reported
method was implemented by those authors to solve their by Nishi (1975), was used to find the values of the
model for the mole fraction and temperature profiles parameters for their activity coefficient model, and those
corresponding to the salt-containing system. The results values were, therefore, used to simulate the dehydration
obtained with the use of salt were compared with those column operated at 0.25 atm. No account was given by
of the salt-free system. those authors on how such a change in pressure basis for
An innovating process flowsheet, to produce absolute the VLE calculations could affect their simulation
ethanol from dilute ethanol /water solutions, optimized results. Moreover, since the ethanol /water azeotrope
for heat integration, and consisting of a preconcentra- can be eliminated by the sole cause of lowering the
tion column (with intermediate heat pumps and optimal pressure to 0.11 atm, according to Black (1980), then the
side-stream return), a saline extractive distillation col- production of hyperazeotropic ethanol by saline extrac-
umn (using potassium acetate as separating agent), a tive distillation at 0.25 atm is not due entirely to the
salt-concentrating evaporator, and a spray dryer, was salting out effect of CaCl2.
proposed and described in detail by Lynd and Grethlein A procedure for the production of absolute ethanol
(1984). It was shown by those authors that such a using CaCl2 as separating agent was devised and
process involves lower capital costs and substantial patented by Zeitsch (1989). The flowsheet for his process
energy savings as compared with conventional separa- consists of a steam-stripping preconcentration column
tion schemes used to make absolute ethanol. operated at atmospheric pressure, a saline extractive
The successful use of calcium chloride (CaCl2) as an distillation (or dehydration) column operated at sub-
agent to remove the ethanol /water azeotrope, was atmospheric pressure (0.34 atm), a two-stage vacuum
experimentally shown and evaluated by Barba, Bran- evaporator, a spray tower, and a drum dryer; the latter
dani and di Giacomo (1985) in a packed column. They three of these process units being needed for recovery of
reported a flowsheet of the process for industrial the anhydrous salt. The overhead vapor of the pre-
production of hyperazeotropic ethanol (with a concen- concentration column is fed to the dehydration column
tration as high as 99.3 wt.%), consisting of a preconcen- whose reflux is ethanol saturated with CaCl2.
tration column, a saline extractive distillation (or Another attempt to simulate saline extractive distilla-
dehydration) column operated at subatmospheric pres- tion columns for the production of hyperazeotropic
sure (0.25 atm), a vacuum evaporative crystallizer and a ethanol (with a concentration as high as 98.95 mol%) at
spray dryer; the latter two of these process units being atmospheric pressure was made by Cespedes and
needed for recovery of the anhydrous salt. The overhead Ravagnani (1995). Three salts were tested as separating
vapor of the preconcentration column is fed to the agents: LiCl, CaCl2, and potassium acetate. For the
dehydration column. Those authors, partly on the basis calculation of the material and energy balances, and the
of previous studies made by Black and Ditsler (1972), VLE behavior, the salt-containing liquid mixture was
Black (1980), compared the energy consumption of their treated as a pseudo-binary system, and the UNIQUAC-
dehydration process using CaCl2 with some of the E model by Sander, Fredenslund and Rasmussen (1986)
conventional azeotropic (using benzene, pentane or was used for the calculation of activity coefficients for
the pseudo-components ethanol and water. No valida- provides the largest salting out effect on ethanol and
tion of the predicted phase equilibrium behavior was that saline extractive distillation (using CaCl2) has a
made by Cespedes and Ravagnani. Also, the model of lower energy consumption as compared with conven-
the distillation column was not presented in detail. tional extractive distillation (using ethylene glycol).
However, those authors stated that their model ignores The aim of this work is to propose a rigorous steady-
the contribution of the salt to the energy balances, and state equilibrium-stage model of saline extractive dis-
also that a simultaneous correction procedure based on tillation columns on the basis of normalized MESH
the Newton /Raphson method was implemented to equations and numerically simulate it for the particular
solve the model for the mole fraction profiles of ethanol case of the production of absolute ethanol at atmo-
and the salt. It was shown by Cespedes and Ravagnani spheric pressure using CaCl2 as separating agent. The
that among the three salts considered, CaCl2 provides choice of CaCl2 is due to the fact that, according to the
the largest salting out effect on ethanol and allows the previous works, it provides the largest salting out effect
use of a minimum number of separation stages. on ethanol, and also because not only the required VLE
More recently, Pinto, Wolf-Maciel and Lintomen data but also experimental data or published correla-
(2000) reported a simulation study of both conventional tions for the calorimetric properties are available for the
(using ethylene glycol) and saline extractive distillation ternary system ethanol/water/CaCl2 or the binary sys-
for ethanol purification, carried out with the help of a tem water/CaCl2, respectively, in contrast to the ethanol/
commercial process simulation package. Four salts were water/potassium acetate system for which only VLE
tested as separating agents: NaCl, KCl, KI, CaCl2. The data can be found in the open literature. To demonstrate
main set of input data, specified parameters, and output the azeotrope-breaking capability of the salt effect on its
data (such as stage temperature and composition own (without the help of a lowered pressure), an
profiles) reported for the saline extractive distillation atmospheric pressure operation is chosen for the simu-
process, were given for the case in which NaCl is used as lation of the column.
separating agent. According to the results so reported, To ensure the reliability of the results to be obtained,
NaCl was shown to be entirely capable of removing the a validated choice is made not only about the para-
ethanol /water azeotrope at 1 atm. Surprisingly, this meters of the activity coefficient model to be used for the
turns out to be contrary to the experimental evidence VLE calculations, but also about all the correlations for
given long time ago by Johnson and Furter (1960) about thermophysical properties required to implement the
the actual inability for NaCl to eliminate this azeotrope mathematical model of the column, which is presented
even at a high concentration, corresponding to satura- in Section 2. As shown in Section 3, the NRTL-E model
tion of the salt in the ethanol /water solution (as by Mock, Evans and Chen (1986) was found to be the
indicated by the VLE curve given as Fig. 3 in Johnson most accurate (among the activity coefficient models
and Furter’s paper). Looking at the corresponding available for mixed solvent/salt systems) to correlate the
experimental VLE curve (Fig. 4 in Johnson and Furter’s experimental VLE data available for the ethanol/water/
paper) the same inability had been shown to be CaCl2 system. However, to adapt the VLE model to the
exhibited by KCl. In contrast, KI had been shown to model of the column, and to obtain at the same time an
be capable of eliminating the azeotrope, but only at accurate correlation, it was necessary to refit some of the
saturation, as indicated in Fig. 7 of a later paper by parameters of the NRTL-E model as to reproduce the
Meranda and Furter (1972). The inconsistency between experimental vapor composition and boiling tempera-
the experimental evidence available for NaCl and the ture of the ternary system with a sufficiently low
simulation results obtained by Pinto, Wolf-Maciel and absolute average deviation. Also, a convenient modeling
Lintomen might be related to the use of values not approach (devised by the corresponding author of this
entirely validated for the parameters of the activity paper), is presented in Section 4 to account in a proper
coefficient model (NRTL-E) that was chosen by those way for the contribution of the salt to the enthalpy of
authors to calculate VLE ratios. Such an explanation the liquid streams in the distillation column. A very
becomes very likely by considering the discussion useful expression is derived to calculate that contribu-
presented by Carlson (1996), and more recently by tion by combining known calorimetric quantities for the
Agarwal, Li, Santollani, Satyro and Vieler (2001), about solute such as its relative apparent enthalpy and the
the potential dangers involved in the choice of physical values at infinite dilution of its integral heat of solution
property correlations and thermodynamic model para- and partial isobaric heat capacity. The model of the
meters for process simulation. The importance of column is solved by use of the modified Newton/
validating the phase equilibrium models used for plant Raphson method with a damping factor found by
simulation has also been emphasized by Horwitz and minimizing the Euclidean norm of the vector of
Nocera (1996). In spite of the unexpected results for discrepancy functions associated with the MESH equa-
NaCl, it was shown by Pinto, Wolf-Maciel and Linto- tions. In Section 5, simulation results are presented for
men, in agreement with previous works, that CaCl2 the required concentration of the salt fed into the reflux
stream, for the reflux ratio, and for the number of

equilibrium stages needed to obtain absolute ethanol as
distillate, from a feed corresponding to the overhead
product of a steam-stripping column typically used in
industry to preconcentrate the fermentation broth. The
calculated temperature profile, as well as the liquid and
vapor composition and flow rate profiles, are reported.
Also, the required reboiler heat load is given and
compared with results from previous works.
Fig. 2. General saline extractive distillation stage.
2. Mathematical model of the column energy balance. For the exact meaning of all symbols
used hereafter, please refer to the Nomenclature.
The column shown in Fig. 1 was used in the The five kinds of equations (known as MESH
development of the general model equations. It consists equations) that are required for the steady-state column
of N stages with the total condenser as stage 1 and the trays (i.e. for stages j/2, . . ., N/1) are formulated as
partial reboiler as stage N . The pressure in the column is follows:
assumed to be constant. The stages of the column,
1) Overall material balance at stage j:
shown in Fig. 2, are assumed to be steady-state ideal
stages, that is, temperature and composition are as- Lj1 Vj1 Fj (Lj Uj )(Vj Wj )0; (1)
sumed to be independent of time and uniform at each
2) Material balance for component i at stage j:
stage, and the liquid and vapor streams leaving any
given stage are assumed to be in thermodynamic phase Lj1 xi;j1 Vj1 yi;j1 Fj zi;j (Lj Uj )xi;j
equilibrium. (Vj Wj )yi;j
In the modeling approach chosen for this work, five
kinds of equations are required for a complete descrip- 0 (2)
tion of each stage: the overall material balance, the 3) VLE relationship for component i at stage j:
component material balances, the VLE relationship for
Ki;j xi;j yi;j 0 (3)
each component, the stoichiometric constraints, and the
4) Stoichiometric constraint at stage j:
X
C
(xi;j yi;j ) 0 (4)
i1
5) Energy balance around stage j:

Lj1 hL;j1 Vj1 hV;j1 Fj hF;j (Lj Uj )hL;j
(Vj Wj )hV;j Qj
0 (5)
All the feed-stream flow rates Fj , the liquid Uj and

vapor Wj side-stream flow rates, and the heat loads Qj
should be specified variables for stages j /2, . . ., N/
1. As shown in Fig. 3, for the production of absolute
ethanol, there is only one stream naturally fed to the
column, and there are no liquid or vapor side streams
leaving or entering the column trays. Also, adiabatic
operation is assumed for each of the trays of the column.
Since the salt is non volatile, it is present only in the
liquid phase, and in consequence, vapor mole fractions
and the VLE relationship are required only for ethanol
and water. Given that the distillate is formed by
condensing a salt-free overhead vapor, no salt is
Fig. 1. General configuration for saline extractive distillation column. naturally present in the reflux stream returned to the
1) Overall material balance discrepancy function at

stage j:
Lj1 Vj1 Fj
Mj 1 (6)
(Lj Uj ) (Vj Wj )
2) Material balance discrepancy function for compo-
nent i at stage j:
Lj1 xi;j1 Vj1 yi;j1 Fj zi;j
Mi;j 1 (7)
(Lj Uj )xi;j (Vj Wj )yi;j
3) VLE relationship discrepancy function for compo-
nent i at stage j:
Ei;j Ki;j xi;j yi;j (8)
4) Stoichiometric constraint discrepancy function at
stage j:
X
C
Sj (xi;j yi;j ) (9)
Fig. 3. Column specifications for simulation run reported in this study. i1
5) Energy balance discrepancy function at stage j :
column. In the actual industrial or pilot-plant imple- Lj1 hL;j1 Vj1 hV;j1 Fj hF;j
Hj 1 (10)
mentation of a saline extractive distillation column, the (Lj Uj )hL;j (Vj Wj )hV;j Qj
anhydrous salt is recovered from the aqueous bottom
product and recycled to be dissolved into the hot water-
free reflux stream before entering the column. However, Eqs. (6), (7) and (10) are similar to the normalized
for convenience in the development of a mathematical equations given by Haas (1992) for the Naphtali /
model of the column, a virtual stream F2 (with all the Sandholm method. For stages j/2, . . ., N/1, the
properties of the dissolved solute) is fed to the stage at following correspondence scheme is chosen between
the top of the column as shown in Fig. 3, entering iterated variables and discrepancy functions:
separately from the corresponding solvent which is V j l Mj ; yi;j l Ei;j ; Tj l Hj ; xi;j l Mi;j ;
considered as the actual reflux stream L1. (11)
Lj l Sj
When the set of MESH equations is solved by a
simultaneous correction procedure (like the Newton / In this work, the energy balances for the condenser
Raphson method) convergence is achieved when the and the reboiler are used, after convergence is achieved,
left hand sides of the equations are sufficiently close to to compute the corresponding heat duties Q1 and QN .
zero. The left hand side of an equation is then usually Therefore, these two energy balances have to be
employed to define a residual or discrepancy function. replaced by two other discrepancy functions. Since the
The goal in the solution procedure is to drive the values liquid streams leaving both the condenser and the
of all discrepancy functions to within some tolerance of reboiler should be at their corresponding bubble points,
zero (Seader & Henley, 1998). a suitable discrepancy function Hj to be used instead of
One natural way to decide on the convergence of the the energy balances for the condenser and the reboiler, is
iterative procedure is by calculating the Euclidean norm the following:
of the vector of discrepancy functions, which is defined X
C
as the square root of the sum of the squares of the Hj Ki;j xi;j 1 (12)
functions. However, for this norm to be mathematically i1
meaningful, the components of the vector should be By definition, for a total condenser, the total vapor
dimensionless. In consequence, it is convenient to flow rate V1 and the vapor phase mole fractions yi ,1 are
normalize all the MESH equations, forcing them to be equal to zero, and therefore, all these variables can be
of the same order of magnitude. Among the many ways eliminated as iterated variables. In consequence, the
in which such a normalization could be made, it was overall material balance M1 (which involves V1) and the
decided for the present work to define the normalized VLE relationships Ei ,1 (which involve the mole fractions
discrepancy functions (for stages j /2, . . ., N/1) as yi ,1) can be eliminated as discrepancy functions for stage
follows: 1. Also, the stoichiometric constraint (which involves
the mole fractions yi ,1) should be replaced by another J(k) DX(k) F(k) ; (20)
constraint, more conveniently related to one specifica-
tion at the top of the column. It is natural to specify the where J /@F/@X is the Jacobian matrix or (n /n )
distillate flow rate U1 and the reflux flow rate. Let L1 be matrix of partial derivatives of all the discrepancy
the specified reflux flow rate and L1 be the iterated functions with respect to all the iterated variables, and
reflux flow rate. Then, the substitute constraint for the DX is the vector of corrections to the iterated variables,
condenser may be written as: which is used to compute the next approximation to the
solution from the recursion formula:
L1
S1 1 (13)
L
1 X(k1) X(k) tDX(k) ; (21)
Thus, for the condenser the following correspondence
scheme is chosen between iterated variables and dis- where t is a damping factor. When t/1, the original
crepancy functions: Newton/Raphson method is used. Sometimes, it is
found to be convenient to choose a value of t "/1 to
T1 l H1 ; xi;1 l Mi;1 ; L1 l S1 (14) ensure the convergence of the algorithm, which is then
By writing an overall material balance around the known as the modified Newton/Raphson method.
column, it is possible to find the specified value for the In this work, the accurate and robust Gauss /Jordan
bottom product flowrate: method of elimination with partial pivoting and column
rescaling (Burden & Faires, 1993) was used to solve the
X
N1
system of linear algebraic equations given by Eq. (20).
LN (Fj Uj Wj )U1 V1 (15) The elements of the Jacobian matrix were evaluated at
j2
each iteration by means of numerical perturbation
Therefore, for the reboiler, the stoichiometric con-
straint given by Eq. (9) is replaced by a specification @fi fi (xi ; xj o) fi (xi ; xj )
: ; (22)
constraint analogous to Eq. (13): @xj o
LN
SN 1 (16) with o /10 3Dxj (Holland, 1981). The damping factor t
L
N
was found by minimizing the Euclidean norm of the
For the reboiler, the correspondence scheme given by vector of discrepancy functions defined as:
Eq. (11) is used with HN and SN being replaced by Eqs.
(12) and (16), respectively. X
n
To implement the Newton /Raphson method, a ½½F(t)½½ fj 2 1=2
(23)
j1
vector of iterated variables X is defined by combining
the variables of all the stages, and a vector of discre-
pancy functions F is defined by combining the functions This norm turns out to be a function of a single
of all the stages, as follows: variable, the damping factor t. The minimization of the
norm was performed by use of Davidon’s two-point
X [T1 ; xi;1 ; L1 ; Vj ; yi;j ; Tj ; xi;j ; Lj ; VN ; yi;N ; cubic interpolation method for one-dimensional optimi-
TN ; xi;N ; LN ]T (17) zation, in the way described by Fletcher and Powell
F [H1 ; Mi;1 ; S1 ; Mj ; Ei;j ; Hj ; Mi;j ; Sj ; MN ; (1963), and discussed in detail by Fox (1971).
The success of the Newton/Raphson method depends
Ei;N ; HN ; Mi;N ; SN ]T (18) on the starting guesses for the iterated variables.
where j /2, . . ., N/1. Following a suggestion made by Haas (1992), the
The k -th iteration of the Newton /Raphson method is tridiagonal matrix method by Wang and Henke (1966)
performed by solving the following system of linear was used in this work to generate the initial profiles for
algebraic equations: temperature, composition and flow rates, taking into
account, right after the first iteration, the liquid phase
Xn
@fi (k) non-ideality for the computation of VLE ratios. The
Dxj (k) fi (k) ; for i 1; 2; . . . ; n (19) Thomas algorithm for tridiagonal systems of linear
j1 @xj
equations, as explained in detail by Seader and Henley
where n/2(C/1)(N/1)/(C/1) is the number of (1998), was used to implement the Wang /Henke
iterated variables (or discrepancy functions), with C as method. Use of a flexible number of iterations for the
the number of components (which is equal to 3 in the Wang/Henke method allowed the starting profiles for
column model simulated in the present work). In matrix the Newton/Raphson method to vary in such a way as
form, this system of equations may be written as (Seader to attain a faster reduction for the Euclidean norm of
& Henley, 1998): the vector of discrepancy functions.

3. Vapor /liquid equilibrium (VLE) model Fermeglia & Rasmussen, 1991). In all three models, the
salt is assumed to be completely dissociated in solution
The VLE ratio Ki,j may be written in general as forming the corresponding ionic species (cations and
(Prausnitz, Eckert, Orye, & O’Connell, 1967): anions). Sometimes, the ions may interact with the
molecules of the solvent species in such a way as to
yi;j exhibit preferential solvation by one of the solvents
Ki;j
xi;j (usually the less volatile) and salting out of the other
solvent (usually the more volatile), as shown by the
g P sat
i;j i;j experimental behavior of the ethanol/water system in the
P presence of some salts (like potassium acetate and
sat sat calcium chloride).
8 i;j n
exp i;j (PPi;j sat ) ; (24)
8̂ i;j RTj
3.1. Correlation results with the NRTL-E model
where i refers only to ethanol or water in the model of
the column, since a VLE relationship is not required for In adapting the NRTL-E model for mixed solvent
the non volatile salt. electrolyte systems, Mock et al. (1986) decided to drop
At low pressures, the virial equation of state, trun- the long-range ion /ion contribution from the model for
cated after the second virial coefficient, may be used to the total Gibbs free energy of the system, from the
compute both the partial and the saturated pure consideration that the model should be tailored to
component fugacity coefficients 8̂ i;j and 8sat represent the phase equilibrium behavior of the solvent
i ,j . A general-
ized method, such as the correlation by Hayden and mixture. Therefore, only the activity coefficients of the
O’Connell (1975), described in detail by Prausnitz, solvents matter for the VLE calculations. However, it
Anderson, Grens, Eckert, Hsieh and O’Connell (1980), was not explicitly stated by those authors whether true
may be used to predict the values for the corresponding mole fractions (for the quaternary system solvent 1/
second virial coefficients. Also, the saturated liquid solvent 2/cations/anions) or apparent mole fractions (for
molar volumes may be estimated by the use of an the ternary system solvent 1/solvent 2/non dissociated
approximation such as Rackett’s equation, as modified salt) should be involved in the expression for the VLE
by Spencer and Danner, in the form given by Prausnitz ratios, Eq. (24). Since, as explained in Sections 2 and 4,
et al. (1980). If the term inside the key brackets in Eq. the material and energy balances are written for the
(24) is then computed for the binary system ethanol/ ternary system solvent (1)/solvent (2)/non dissociated
water at the vapor compositions and temperatures salt (3) in the column model of this work, then it would
corresponding to the bubble point states of the mixture be convenient to define the liquid mole fractions of
(at a pressure of 1 atm), values close to unity are ethanol and water in Eq. (24) on the basis of the ternary
obtained for that term. system ethanol/water/CaCl2, even though the calcula-
It was then decided for computational convenience (as tion of the activity coefficients of the two solvents
suggested by Agarwal et al., 2001), to absorb the small requires the true mole fractions of the four species
effect of that term in disguise inside the regressed values ethanol (m1), water (m2), Ca 2 ions (c), and Cl 1 ions
for the interaction parameters of the activity coefficient (a ), as shown in Appendix A. As explained below, this
model being used. This practice has already shown to be modeling choice requires a refitting of the parameters
successful by Gmehling and Onken (1977) when regres- for the NRTL-E model from the values that were
sing parameters for the DECHEMA VLE data collec- reported by Mock, Evans and Chen for the ternary
tion. system ethanol/water/CaCl2.
In this way, the VLE ratio is simplified to the As shown in Appendix A, the NRTL-E model
expression: requires nine parameters for the ternary system ethanol
(m1)/water (m2)/CaCl2 (ca ). Following Chen and Evans
gi;j Pi;j sat (1986), Mock et al. (1986) decided to set the non-
Ki;j (25)
P randomness factor of the water/CaCl2 system to an
arbitrary value of aca ,m2 /0.2. From the experimental
The correlation used in this work to calculate the osmotic coefficient data reported by Robinson and
vapor pressures of ethanol and water is reported in Stokes (1970) for aqueous CaCl2 solutions at 25 8C,
Appendix C. Mock, Evans and Chen obtained the values of tca ,m2 /
For VLE in mixed solvent/salt systems, there are three /5.848 and tm2,ca /11.623 for the remaining para-
activity coefficient models more frequently cited in the meters of the water/CaCl2 system. From VLE data for
literature: NRTL-E (Chen & Evans, 1986; Mock et al., the ethanol/water system (at a pressure of 1 atm) taken
1986), UNIQUAC-E (Sander et al., 1986; Macedo, from a literature source not specified in their paper,
Skovborg & Rasmussen, 1990), and UNIFAC-E (Kikic, Mock, Evans and Chen obtained the values of am1,m2 /
0.3, tm1,m2 //0.1341, and tm2,m1 /1.8224 for the three were obtained for the average absolute deviations (with
parameters of the mixed solvent system. From the respect to the experimental data) of the boiling tem-
experimental VLE data reported by Nishi (1975) for perature of the system and the vapor mole fraction of
the ethanol/water/CaCl2 system, Mock, Evans and Chen ethanol. The deviation so obtained for the vapor mole
obtained the values of aca ,m1 /0.06, tca ,m1 //13.928 fraction of ethanol is much lower than the deviation
and tm1,ca /25.032, for the three parameters of the jDy1j /0.0240 reported by Mock, Evans and Chen in
ethanol/CaCl2 system. their paper. This dramatic reduction in the vapor mole
In this work, the parameter values obtained by Mock, fraction deviation is crucial for a reliable simulation of
Evans and Chen for the water/CaCl2 and the ethanol/ the production of absolute ethanol by saline extractive
water systems were retained. However, the parameters distillation and supports this work’s choice of apparent
for the ethanol/CaCl2 system were fitted again to the liquid mole fractions for the calculation of VLE ratios.
experimental VLE data reported by Nishi (1975) for the As shown in Fig. 4, the ethanol /water azeotrope at 1
ethanol/water/CaCl2 system (at a pressure of 1 atm and atm (with a composition of approximately 89 mol% of
a salt concentration of 16.7 wt.%, on a salt-free basis), to ethanol) disappears in the presence of CaCl2 at a
reproduce the experimental vapor composition and concentration of 16.7 wt.% on a salt-free basis. As
boiling temperature of the ternary system with a explained by Sander et al. (1986), a phase diagram like
sufficiently low absolute average deviation, and also to the one shown in Fig. 5, may seem, at first sight, to be
be consistent with the modeling choice made for the entirely erroneous because a crossing point in a tem-
mole fractions used in Eq. (24), as explained above. The perature vs. composition diagram tends to be associated
objective function for regressing the parameters was with the occurrence of an azeotrope. However, it should
defined as the sum of squared deviations (with respect to be noticed that the phase behavior of the ternary system
the experimental data) of the values predicted by the is plotted in Fig. 5 as if it were a binary system. If the
model for the boiling temperature and the vapor equilibrium vapor and liquid phase compositions are
composition. The flexible polyhedron method for multi- followed from one end of the diagram to the other (with
dimensional optimization by Nelder and Mead (1965), the help of Table 1), it is found that the crossing point
as explained in detail by Himmelblau (1972), was used between the bubble point and dew point curves does not
to obtain the optimum values of the parameters, which correspond to coexisting liquid and vapor phases and, in
turned out to be as follows: aca ,m1 /0.0293, tca ,m1 // consequence, it is not an azeotropic point. Actually, as
25.4824 and tm1,ca /51.4988. shown in Fig. 4, the azeotrope has been completely
For a salt-free system, the NRTL-E model by Mock eliminated by the salting out effect of CaCl2 on ethanol.
et al. (1986) reduces to the original NRTL model by
Renon and Prausnitz (1968) for non-electrolyte systems. 3.2. Prediction results with the UNIQUAC-E and
The experimental VLE data set at 1 atm, obtained by UNIFAC-E models
Rieder and Thompson (1949) (which is also available
from the DECHEMA VLE data collection by Gmehling The UNIQUAC-E (Sander et al., 1986; Macedo et al.,
and Onken, 1977), was used in this work to validate the 1990), and UNIFAC-E (Kikic et al., 1991) models were
values of the parameters obtained by Mock, Evans and also tried in an attempt to reproduce the experimental
Chen for the ethanol/water system, obtaining a very VLE data reported by Nishi (1975) for the ethanol/
accurate fit as shown in Fig. 4 (dotted line and empty water/CaCl2 system, yielding results not as successful as
circles). Values of jDT j /0.16 8C and jDy1j / for the NRTL-E model. Since this ternary system was
0.0087 were obtained for the average absolute deviations not included in the database compiled for the develop-
(with respect to the experimental data) of the boiling ment of the UNIQUAC-E and UNIFAC-E models,
temperature of the system and the vapor mole fraction then the results obtained from these models should be
of ethanol. considered a prediction rather than a correlation
The entire set of parameters for the ethanol/water/ exercise. The parameters reported for these models by
CaCl2 system, that includes the refitted set for the their authors were found from a fit of the models to the
ethanol/CaCl2 system, was validated against the experi- available experimental VLE data of many other mixed
mental VLE data reported by Nishi (1975). An accurate solvent/electrolyte systems, using true mole fractions
fit was obtained as shown numerically in Table 1, and (for the quaternary system solvent 1/solvent 2/cations/
also graphically, in Fig. 4 for the y1 versus x1? equili- anions) for the calculation of VLE ratios. In conse-
brium curve (solid line and filled circles), and in Fig. 5 quence, these two models were originally cast in a form
for the T versus x1?, y1 diagram. It should be noticed that that is not in accordance with the choice of apparent
for plotting both figures, the mole fraction of ethanol in liquid mole fractions made in this work for the calcula-
the liquid phase is calculated on a salt-free basis (that is tion of VLE ratios. In spite of this fact, it might still be
indeed the meaning of the note used as a superscript for of some interest to compute the average deviations
x1). Values of jDTj /0.31 8C and jDy1j /0.0068 yielded by the two models for the VLE behavior of the
Fig. 4. VLE diagrams for the ethanol (1)/water (2) system (empty circles, experimental data; dotted line, calculated from NRTL model) and for the
ethanol (1)/water (2)/CaCl2 (3) system (filled circles, experimental data; solid line, calculated from NRTL-E model). x1? is the mole fraction of ethanol
on a salt-free basis.
ternary system ethanol/water/CaCl2, using the true mole for UNIFAC-E, taking into account the temperature
fractions approach as required for these models. dependency of the densities of the pure components. Use
For the UNIQUAC-E model, values of jDT j / of Oster’s empirical mixing rule (according to the
1.38 8C and jDy1j /0.0106 are obtained for the prescription given by the authors of those models) for
average absolute deviations (with respect to the experi- estimating the dielectric constant of the solvent mixture
mental data) of the boiling temperature of the system with the values of the dielectric constants of the two
and the vapor mole fraction of ethanol, respectively. For solvents at 25 8C (i.e. neglecting the temperature
the UNIFAC-E model, values of jDT j /1.11 8C and dependency of the dielectric constants), yields results
jDy1j /0.0343 are obtained for the same quantities. that show slightly lower deviations for the UNIQUAC-
These results were obtained by considering the tempera- E model: jDT j /0.93 8C and jDy1j /0.0096, and
ture and composition dependency of the dielectric almost the same deviations for the UNIFAC-E model:
constant of the solvent mixture experimentally obtained jDT j /1.10 8C and jDy1j /0.0361.
by Åkerlöf (1932). The density of the solvent mixture As can be noticed, the average deviations obtained
was computed by means of the approximate ideal from the UNIQUAC-E and UNIFAC-E models are
solution scheme prescribed in common by Macedo et higher than those obtained from the adapted NRTL-E
al. (1990) for UNIQUAC-E, and by Kikic et al. (1991) model. In particular, the temperature average deviation
Table 1
Comparison of results obtained from the NRTL-E model with experimental data by Nishi (1975) for the VLE of ethanol (1)/water (2)/CaCl2 (3) (at a
pressure of 1 atm and a salt concentration of 16.7 wt.% on a salt-free basis), x1? is the mole fraction of ethanol on a salt-free basis
x1? y1 (experimental) y1 (calculated) Dy1 T (experimental) (8C) T (calculated) (8C) DT (8C)
0.000 0.000 0.000 0.000 102.80 103.69 0.89

0.020 0.271 0.264 0.007 96.00 95.92 0.08
0.040 0.389 0.394 0.005 91.60 91.41 0.19
0.100 0.542 0.558 0.016 85.00 85.16 0.16
0.200 0.647 0.651 0.004 82.45 82.10 0.35
0.300 0.694 0.701 0.007 81.45 81.30 0.15
0.400 0.753 0.743 0.010 81.25 81.11 0.14
0.500 0.795 0.785 0.010 80.70 81.14 0.44
0.600 0.828 0.829 0.001 81.50 81.27 0.23
0.700 0.867 0.872 0.005 81.50 81.47 0.03
0.800 0.915 0.916 0.001 82.40 81.72 0.68
0.900 0.942 0.959 0.017 81.65 82.02 0.37
Fig. 5. Temperature-composition diagram for the ethanol (1)/water (2)/CaCl2 (3) system (filled circles, experimental data; solid line, calculated from
NRTL-E model). x1? is the mole fraction of ethanol on a salt-free basis. As explained in the text, the crossing point does not correspond to coexisting
liquid and vapor phases and, in consequence it is not an azeotropic point. Actually, the azeotrope has been eliminated by the salting out effect of
CaCl2 on ethanol, as shown in Fig. 4.
obtained from both models and the mole fraction experimentally determined for some ions, as discussed
average deviation obtained from UNIFAC-E turn out by Marcus (1997). Therefore, a different approach to the
to be unacceptably high. In consequence, the NRTL-E calculation of the liquid enthalpy of mixed solvent/
model was chosen for the VLE calculations that are electrolyte systems is required. One of the aims of this
required for the solution of the mathematical model of work is precisely to propose such an approach and
the column proposed in this work. implement it for the particular case of the ternary system
ethanol/water/CaCl2.
An expression for the liquid phase enthalpy of the
ternary system solvent (1)/solvent (2)/salt (3) can be
4. Enthalpy model for mixed solvent/salt systems derived by considering an overall process consisting of
two steps: the mixing of the two solvents, and the
A liquid enthalpy model for aqueous/salt systems dissolution of the salt (the solute) into the binary solvent
based on ion properties was discussed by Liu and mixture.
Watanasiri (1999). The model requires the aqueous The enthalpy change for the first step is known as
enthalpy of formation of the ions at infinite dilution at heat of mixing (or excess enthalpy) and is given by:
25 8C, and the aqueous isobaric heat capacity of the
ions at infinite dilution as a function of temperature. H E Hm (2) n1 h1 n2 h2 (26)
These ion properties have already been experimentally
where H(2)
m is the enthalpy of the binary solvent mixture,
determined for some ions and their values at 25 8C have
and h1 and h2 are the pure component molar liquid
been critically reviewed and compiled by Marcus (1997).
enthalpies of the two solvents.
As pointed out by Liu and Watanasiri, property
If Eq. (26) is divided by the total solvent mole number
methods for non-aqueous electrolyte systems are not
n1/n2, then the following expression is obtained for the
as well developed as those for aqueous electrolytes, and
molar enthalpy of the binary solvent mixture:
process simulators have just begun to address this need.
In principle, it could be possible to adapt the enthalpy hm (2) x?1 h1 x?2 h2 hE (27)
model discussed by Liu and Watanasiri to mixed
solvent/electrolyte systems. For that purpose, it would where x1? /x1/(x1/x2) and x2? /x2/(x1/x2) are the mole
be necessary to have available the enthalpies for the fractions of the two solvents on a salt-free basis, and hE
transfer of the ions from the state of infinite dilution in is the molar heat of mixing of the binary solvent
aqueous solution to the state of infinite dilution in the mixture.
mixed solvent solution. So far, only the enthalpies of The enthalpy change for the second step, the dissolu-
transfer from water to single solvents have been tion of n3 moles of solute into n1/n2 moles of solvent
mixture, is known as integral heat of solution and is Substitution of Eq. (36) into Eq. (34) gives:
given by: T
g c̄
i (3) (2) i; i;
DHsol Hm Hm n3 h3 (28) Dhsol (T) Dhsol (T0 ) p;3 (T)dT
where H(3)
is the enthalpy of the ternary mixture and h3
m
T0
is the pure component molar enthalpy of the non- [h3 (T)h3 (T0 )] (37)
dissolved salt. Written entirely on a molar basis, Eq. (28)
becomes: Finally, substitution of Eq. (37) into Eq. (33) yields:
n3 Dhsol i (n1 n2 n3 )hm (3) (n1 n2 )hm (2) n3 h3 (29) hm (3) (T)[x1 h1 (T)x2 h2 (T)(1x3 )hE (T)]

If Eq. (29) is divided by the total mole number n1/ x3 h3 (T0 )fL3 (T)Dhsol i; (T0 )
n2/n3, then the following expression is obtained for the
molar enthalpy of the ternary mixture: T
(3) (2)
hm (x1 x2 )hm x3 (h3 Dhsol ) i
(30)
g
T0
c̄p;3 (T)dT (38)
Substitution of Eq. (27) into Eq. (30) and use of the

defining expressions for x1? and x2? yields: Actually, if all the independent variables on which the
thermophysical properties depend are explicitly shown,
hm (3) (T)[x1 h1 (T)x2 h2 (T)(1x3 )hE (T)]
Eq. (38) takes the form:
x3 [h3 (T)Dhsol i (T)] (31)
hm (3) (T; x?1 ; m)
where, for now, only dependency on temperature T is
explicitly shown for all the thermophysical properties. [x1 h1 (T)x2 h2 (T)(1x3 )hE (T; x?1 )]

Eq. (B12), derived in Appendix B for a binary system
x3 h3 (T0 )fL3 (T; x?1 ; m)Dhsol i; (T0 ; x?1 )
solvent (1)/solute (2), may be extended to the ternary
system solvent (1)/solvent (2)/solute (3) by simply T
rewriting that expression in the form:
Dhsol i (T)fL3 (T)Dhsol i; (T) (32)

T0
g c̄p;3 (T; x?1 )dT (39)
Substitution of Eq. (32) into Eq. (31) gives: Eq. (39) summarizes the model proposed in this work
(3)
hm (T)[x1 h1 (T)x2 h2 (T)(1x3 )h (T)] E to calculate the liquid phase enthalpy h(3) m (T , x1?, m ) in
mixed solvent/salt systems. This model requires as
x3 [h3 (T)fL3 (T)Dhsol i; (T)] (33) subsidiary properties, the pure component molar liquid
As discussed below, Dhisol ,
is available only at a enthalpies h1(T ) and h2(T ) of the two solvents, the
reference temperature of 25 8C. In consequence, it is molar heat of mixing hE (T , x1?) for the binary solvent
necessary to obtain a relationship between Dhisol
,
(T ) and mixture, the relative apparent molar enthalpy fL3(T , x1?,
i ,
Dhsol (T0), where T0 is the reference temperature. By m ) of the solute, the molar integral heat of solution at
extending Eq. (B11) (derived in Appendix B) to the infinite dilution Dhisol
,
(T0, x1?) measured at the reference
ternary system, writing that equation at temperatures T temperature T0, and the temperature dependency for the
and T0, and making the difference between the resulting partial molar isobaric heat capacity c̄p;3 /(T , x1?) of the
expressions, the following expression is obtained: solute, where x1? is the liquid mole fraction of solvent (1)
on a salt-free basis, and m is the molality of the salt in
Dhsol i; (T)Dhsol i; (T0 ) h̄3 (T) h̄3 (T0 ) the ternary system. The molar enthalpy h3(T0) of the
[h3 (T)h3 (T0 )] (34) non-dissociated pure salt may be equated with zero at
the reference state chosen (pure solid at T0). In
The partial molar isobaric heat capacity of the solute Appendix C, detailed information is given on how to
at infinite dilution is defined as: calculate h1(T ), h2(T ),and hE (T , x1?).
For the molar integral heat of solution at infinite
@ h̄3
c̄p;3 (35) dilution of the solute, Dhisol ,
(T0, x1?), experimental
@T P;fxg
measurements for the ternary system ethanol/water/
Integration of this expression from T0 to T , at CaCl2 were made at the reference temperature of
constant pressure P and composition {x }, yields: 25 8C by Taniewska-Osinska and Barczynska (1984),
T
reporting a table with 18 values for Dhisol ,
(T0, x1?)
corresponding to the entire range of mole fractions x1?
g c̄
T0
p;3

(T)dT h̄3 (T) h̄3 (T0 ) (36)
for ethanol on a salt-free basis. For this work, those
values were fitted to a fifth-degree polynomial obtaining
an average relative error of 0.6%. The resulting poly- so far; and third, the existence of published correlations
nomial correlation is given at the end of Appendix C. for fL (T , m ) and c̄p /(T ). In fact, by using an extension
For the ternary system ethanol/water/CaCl2, a corre- of Pitzer’s ion-interaction formalism, Ananthaswamy
lation was obtained by Zhang, Wang, Shi, Benson and and Atkinson (1985) fitted a comprehensive set of
Lu (1993) for the molar integral enthalpy of dilution at experimental data for the binary system water/CaCl2
the limit of zero concentration of the solute, Dhidil ,
, and obtained correlations for the relative apparent
which is a quantity entirely different from the molar molar enthalpy fL (T , m ) and the partial molar isobaric
integral enthalpy of solution at infinite dilution Dhisol ,
, heat capacity at infinite dilution c̄p /(T ) of CaCl2 in
already defined and given by Eq. (B11). The correlation aqueous solutions, tabulating values for fL (T , m ) in the
for Dhidil ,
was built by Zhang et al. on the basis of the temperature range 0/100 8C and in the salt-concentra-
values calorimetrically measured for the so-called inter- tion range 0.001 /9 molal. In Appendix C, detailed
mediary integral heats of dilution, which are the information is given on how to calculate fL (T , m ) and
enthalpy changes associated with successive additions c̄p /(T ) from the correlations obtained by Ananthas-
of a fixed-composition mixture of the two solvents to an wamy and Atkinson (1985).
initial ternary solution of a certain salt concentration. The decision for model simplification, stated above,
The measurements were made at three values of rests on two assumptions: first, that the molar integral
temperature: 15, 25, 35 8C, and the dilutions were heat of solution at infinite dilution of the solute, Dhisol ,
performed starting from an initial solution with a salt ?

(T0, x1) accounts for most of the salt contribution to the
concentration close to 1 molal. liquid phase enthalpy; and second, that the sum of
As shown by Klotz and Rosenberg (1972), the relative fL (T , m ) and the temperature integral of c̄p /(T ) from
apparent molar enthalpy of the solute fL3 is related to the reference temperature T0 to the temperature of
the molar integral enthalpy of dilution at the limit of interest T , is of the same order of magnitude as the
zero concentration of the solute Dhidil ,
through the sum of fL3(T , x1?, m ) and the temperature integral of
i ,
expression fL3 //Dhdil . Thus, in principle, the corre- c̄p;3 /(T , x1?) from T0 to T .
lation obtained by Zhang et al. looks perfect to compute It would be possible to assess the definite effect of this
the values required for fL3(T , x1?, m ) in Eq. (39). decision only in the future, as correlations (valid at the
However, due to the way in which the composition- temperature and molality ranges encountered in the
dependent coefficients of the correlation were reported, simulation of the column) become available for fL3(T ,
the correlation is strictly applicable only at the three x1?, m ) and c̄p;3 /(T , x1?). For the time being, a provisional
temperature values listed above, and remains valid only justification may be given only for the first assumption
for salt concentrations up to 1 molal. Since the stated above, by measuring the relative importance of
temperatures of the column stages are well above the three properties fL (T , m ), Dhisol ,
(T0, x1?), c̄p /(T ) to
35 8C (in the range 78/129 8C), and the salt concen- the calculation of the salt contribution to the liquid
tration in all liquid streams turns out to be greater than phase enthalpy, as shown in the following section.
1 molal (in the range 1.5 /5.8 molal), as reported in
Section 5, a potential use of the correlation by Zhang et
al. for solving the model of the column, would require 5. Simulation results
making a daring extrapolation, well beyond the validity
limits of the correlation. As a matter of fact, an attempt The broth obtained from biomass fermentation is
to carry out such an extrapolation and implement it for normally a dilute ethanol/water solution, with typically
the column model, yielded unreasonable values of the less than 10 wt.% ethanol (Lynd & Grethlein, 1984). In
liquid phase enthalpy for the lower stages of the column, industry, a steam-stripping column is usually employed
forcing the search for another estimation approach. to preconcentrate this dilute solution to a concentration
In that direction, a decision for model simplification greater than 30 wt.% ethanol, prior to any azeotropic or
had to be made for the sake of simulation feasibility. It extractive distillation step (Lynd & Grethlein, 1984). For
was decided to replace the relative apparent molar instance, for the experimental study of saline extractive
enthalpy fL3(T , x1?, m ) and the partial molar isobaric distillation (using CaCl2 as separating agent) carried out
heat capacity at infinite dilution c̄p;3 /(T , x1?) for CaCl2 by Barba et al. (1985) broth preconcentrated to the
in the binary mixture ethanol/water by fL (T , m ) and range 40 /50 wt.% ethanol, was considered as the feed to
c̄p /(T ) for CaCl2 in aqueous solution, computing fL (T , the saline extractive distillation column. On the basis of
m ) at the salt molality m of the ternary mixture. This these considerations, a feed with a concentration of
decision was motivated by three reasons: first, the failure approximately 40 wt.% ethanol (20% on a molar basis)
to extrapolate the correlation for fL3(T , x1?, m ) obtained was chosen for the simulation study reported in this
by Zhang et al., as explained above; second, the lack of a paper.
correlation for c̄p;3 /(T, x1?), a property for which As discussed in Section 3, the parameters for the
experimental measurements have not even been reported activity coefficient model (NRTL-E) chosen in this work
to compute VLE ratios, were obtained from the experi- Table 2

mental data reported by Nishi (1975) for a CaCl2 Input data, specified parameters, and overall output data for the
concentration of 16.7 wt.% (on a salt-free basis). simulation of the saline extractive distillation column with CaCl2 as
Therefore, to perform a conceptually consistent and separating agent
reliable simulation of the column, the concentration of Input/output data and specified Symbol Value
the salt in the column stages should be kept as close as parameters
possible to that value of 16.7 wt.%. For making this
Input data and specified parameters
possible, a saturated vapor condition is assigned to the
Number of equilibrium stages N 22
feed of the column, following the original description of Main feed stage 16
the saline extractive distillation process given by Gorhan Main feed thermodynamic state Saturated vapor
(1932a,b, 1933, 1934) in his patents, and also the Main feed temperature (8C) TF, 2 94.5
flowsheet description of the processes devised by Barba Main feed molar flow rate F16 100
(kmol/h)
et al. (1985), and by Zeitsch (1989). Accordingly, from
Main feed ethanol mole fraction x1,16 0.2
Eqs. (A29) and (A32) in Appendix A, the mole fraction Main feed water mole fraction x2,16 0.8
of salt in the real-plant water-free reflux stream L1/F2 Salt feed molar flow rate (kmol/ F2 8.315
is set to a value of x3 /0.0648, yielding a molar flow h)
rate of 8.315 kmol/h for the model virtual salt feed Salt feed temperature (8C) TF, 2 78.3
Distillate molar flow rate (kmol/ U1 20
stream F2.
h)
All input data and remaining specification parameters Reflux molar flow rate (kmol/h) L1 120
for the simulation of the column are given in Table 2. Operating pressure (atm) P 1
The mathematical model of the column (presented in Output data
Section 2) that includes the VLE and enthalpy models Ethanol molar flow rate in dis- x1,1 19.9996
(presented in Sections 3 and 4, respectively) was tillate (kmol/h)
translated into a computer program with 1780 lines Water molar flow rate in dis- x2,1 0.0004
tillate (kmol/h)
coded in the FORTRAN 95 programming language. As
Condenser heat duty (kJ/h) Q1 5.469/106
explained in Section 2, the Wang /Henke method is Reboiler heat duty (kJ/h) QN 1.841/106
incorporated into the column model to generate starting Reboiler specific heat duty (kJ/ 1998
guesses for the iterated variables, from which the kg ethanol)
modified Newton/Raphson method proceeds until no
further reduction is achieved for the Euclidean norm of duty for the reboiler. The reboiler heat duty divided by
the vector of discrepancy functions. The simulation run the mass flow of ethanol in the distillate yields an energy
corresponding to the column specified in Table 2, takes requirement of 1998 kJ/kg. It would be interesting to
less than 14 s in a PC with a Pentium III/800 MHz compare this energy requirement with the results of
processor, and consists of 20 iterations for the initializa- previous simulation works. For their entire aqueous
tion phase with the Wang /Henke method and 30 ethanol dehydration plant that includes the preconcen-
iterations for the solution phase with the modified tration column, the evaporative crystallizer and the
Newton/Raphson method. The Euclidean norm is spray dryer, besides the saline extractive distillation
reduced from an initial value of 7.3 /103 at the column with CaCl2, Barba et al. (1985) reported a total
beginning of the initialization phase to a final value of energy requirement of 5021 kJ/kg. Since the energy
4.6 /108 at the end of the solution phase.
requirement for the saline column was not reported by
A number of 22 ideal stages (including the condenser
those authors, a comparison with the result of the
and the reboiler) and an operating reflux ratio (L1/F2)/
present work cannot be made. For a saline column with
U1 /6.42 (as explained in Section 2, for developing the
14 ideal stages, with a vapor feed stream with 10.64
column model, the real-plant reflux stream is splitted
into a virtual salt feed stream with a flow rate F2 and a mol% ethanol at 86 8C, a distillate with 98.95 mol%
solvent stream with a flow rate L1), were found to be ethanol, a reflux stream with 10 mol% of CaCl2, and an
necessary to obtain as distillate practically pure ethanol operating reflux ratio of 1.4, Cespedes and Ravagnani
(99.998 mol%), starting from the specified feed. The (1995) reported a reboiler heat duty that is equivalent to
optimum feed stage location was found to be stage 16. an energy requirement of 2281 kJ/kg, which is 14%
In consequence, the stripping section of the column higher than the energy value obtained in the present
consists of five ideal stages, and the rectifying section work. Finally, for a saline column for which the only
comprises 14 ideal stages. operating condition given is a temperature of 85.8 8C
The required heat loads of the reboiler and the for the feed stream, Pinto et al. (2000), reported an
condenser are reported in Table 2. Since the feed to energy requirement of 2166 kJ/kg, which is 5% lower
the column is a vapor stream, the heat duty for the than the energy value obtained by Cespedes and
condenser is higher (as three times greater) than the heat Ravagnani, and 8% higher than the energy value
obtained in the present work. Due to the differences in from fL and c̄p to the solute enthalpy have opposite
column operating conditions, between the work by signs and when combined add a very small amount to
Cespedes and Ravagnani and the present simulation the value of Dhisol
,
(T0, x1?) The much greater importance
i ,
work, and the fact that the ternary system ethanol/ of Dhsol (T0, x1?) to the calculation of the salt contribu-
water/CaCl2 was treated as a pseudo-binary system by tion to the liquid phase enthalpy, relative to the sum of
those authors for the calculation of the energy balances, fL and the temperature integral of c̄p ; justifies, though
the value of the energy requirement that they obtained is provisionally, the first assumption on which the decision
not strictly comparable with the energy value obtained for model simplification stated in Section 4 was based.
in this work.
The temperature, flow rate and composition profiles
obtained from the simulation run are reported in Table 6. Concluding remarks
3. As can be noticed, the profiles for temperature, liquid/
vapor flow rates, and mole fraction of salt in the liquid Extractive distillation by salt effect has been neglected
phase, turn out to be very flat throughout the eight in the past probably due to the complexity of the highly
uppermost stages of the column. As intended, the mole nonideal phase equilibrium behavior and the difficulty
fraction of salt in the liquid streams remains close to the in modeling thermodynamic properties of mixed sol-
value of 0.0648 required for consistency with the source vent/electrolyte systems. In this work, a rigorous model
of the VLE data, as explained above. In terms of of saline extractive distillation columns has been pre-
molality (computed from Eq. (C23) in Appendix C), sented and solved for the production of absolute
the salt concentration increases from 1.5 in the real- ethanol. According to the simulation results reported
plant reflux stream to 5.8 in the bottom product. in this paper, it is indeed possible from a theoretical
The column profiles obtained for the several con- standpoint to produce water-free ethanol by use of
tributions to the liquid phase enthalpy are given in Table saline extractive distillation with CaCl2 as separating
4. As can be noticed, the heat of mixing hE makes an agent, in agreement with what had already been shown
almost negligible contribution to the enthalpy h(2)
m of the experimentally and from exploratory simulations by
binary solvent mixture, which turns out to be almost other authors. The number of stages and reboiler heat
equal to the ideal solution contribution h(2)
id . Overall, the duty that are required for the separation take on entirely
contribution x3hsolute of the solute to the liquid phase feasible values.
enthalpy h(3)
m is not negligible at all, making approxi- There are some opportunities for future research.
mately a 16% of the total enthalpy. The contributions First, the partial molar isobaric heat capacity at infinite
Table 3
Simulation profiles for temperature, vapor/liquid flow rates, and vapor/liquid mole fractions in the saline extractive distillation column specified in
Table 2 for the production of absolute ethanol using CaCl2 as separating agent
Stage T (8C) V (kmol/h) y1 y2 L (kmol/h) x1 x2 x3 m (mol/kg)
1 78.31 0 0 0 120.00 0.99998 0.00002 0 0

2 82.22 140.00 0.99998 0.00002 130.10 0.93604 0.00005 0.06391 1.482
3 82.22 141.78 0.99995 0.00005 130.09 0.93599 0.00010 0.06391 1.482
4 82.22 141.78 0.99990 0.00010 130.09 0.93585 0.00023 0.06392 1.482
5 82.23 141.77 0.99979 0.00021 130.07 0.93559 0.00049 0.06392 1.483
6 82.23 141.76 0.99954 0.00046 130.04 0.93500 0.00106 0.06394 1.484
7 82.23 141.73 0.99903 0.00097 129.98 0.93377 0.00226 0.06397 1.486
8 82.25 141.66 0.99792 0.00208 129.84 0.93114 0.00482 0.06404 1.490
9 82.27 141.52 0.99558 0.00442 129.55 0.92553 0.01029 0.06418 1.499
10 82.32 141.24 0.99056 0.00944 128.99 0.91352 0.02202 0.06446 1.517
11 82.43 140.67 0.97981 0.02019 127.98 0.88769 0.04734 0.06497 1.556
12 82.63 139.67 0.95662 0.04338 126.58 0.83168 0.10263 0.06569 1.636
13 83.06 138.26 0.90604 0.09396 125.54 0.70767 0.22610 0.06623 1.806
14 84.83 137.23 0.79315 0.20685 124.54 0.41108 0.52216 0.06676 2.355
15 97.75 136.23 0.52263 0.47737 125.64 0.06826 0.86556 0.06618 3.532
16 110.45 137.33 0.20809 0.79191 128.88 0.01362 0.92186 0.06452 3.743
17 115.74 40.56 0.04327 0.95673 129.71 0.00225 0.93365 0.06410 3.788
18 116.81 41.40 0.00705 0.99295 129.89 0.00035 0.93564 0.06401 3.794
19 116.98 41.57 0.00110 0.99890 129.92 0.00005 0.93595 0.06400 3.795
20 117.01 41.60 0.00017 0.99983 129.92 0.00001 0.93599 0.06400 3.795
21 117.09 41.61 0.00003 0.99997 129.52 0.00000 0.93580 0.06420 3.808
22 129.49 41.20 0.00000 1.00000 88.315 0.00000 0.90585 0.09415 5.769
Mole fractions are numbered as ethanol (1)/water (2)/CaCl2 (3).

Table 4
Simulation profiles for the several contributions (in J/mol) to the liquid phase molar enthalpy (as given by Eq. (38)) in the saline extractive distillation
column specified in Table 2 for the production of absolute ethanol using CaCl2 as separating agent
T
Stage h(2)
id hE h(2)
m fL Dhisol
,
(T0) /fT c̄p dT/ x3hsolute h(3)
m
0
1 /35031 0.0 /35031 11789 /91447 /13003 0 /35031

2 /32226 0.0 /32226 12300 /91457 /13979 /5953 /38179
3 /32227 0.1 /32227 12301 /91470 /13979 /5954 /38180
4 /32227 0.2 /32227 12302 /91498 /13980 /5956 /38183
5 /32228 0.3 /32228 12303 /91557 /13980 /5960 /38188
6 /32230 0.7 /32229 12307 /91682 /13981 /5969 /38199
7 /32235 1.6 /32233 12315 /91946 /13982 /5989 /38222
8 /32244 3.3 /32241 12331 /92497 /13985 /6030 /38270
9 /32264 7.3 /32257 12366 /93626 /13991 /6113 /38371
10 /32309 16.5 /32293 12438 /95832 /14004 /6278 /38572
11 /32410 38.8 /32373 12589 /99680 /14030 /6570 /38943
12 /32648 94.3 /32559 12896 /104534 /14082 /6945 /39504
13 /33226 217.4 /33023 13549 /104647 /14191 /6973 /39996
14 /34595 285.7 /34328 15746 /89199 /14641 /5881 /40210
15 /35459 1.4 /35458 22731 /75880 /18078 /4714 /40172
16 /34893 /2.7 /34896 26371 /79623 /21766 /4840 /39736
17 /34580 /1.3 /34581 27775 /80939 /23404 /4908 /39490
18 /34515 /0.3 /34515 28051 /81180 /23741 /4921 /39436
19 /34504 /0.1 /34504 28095 /81218 /23796 /4923 /39427
20 /34503 0.0 /34503 28103 /81224 /23805 /4923 /39426
21 /34489 0.0 /34489 28184 /81225 /23832 /4935 /39424
22 /32423 0.0 /32423 43368 /81225 /27956 /6196 /38619
dilution c̄p;3 /(T , x1?) for CaCl2 in the binary mixture come available for correlating the VLE behavior and the
ethanol/water could be experimentally measured to calorimetric properties involved in the enthalpy model
make unnecessary, for the solution of the column model, for the liquid phase. In that direction, a more challen-
the replacement of that quantity by c̄p /(T ), which is ging task would be the measurement and correlation of
actually meant for CaCl2 in aqueous solution. Second, the calorimetric properties of the quaternary system
the calorimetric measurements made by Zhang et al. ethanol/water/potassium acetate/sodium acetate, in-
(1993) could be supplemented by new measurements at volved in the production of absolute ethanol by the
higher temperatures and salt molalities, to obtain a HIAG process. Given that the VLE behavior at atmo-
correlation for the relative apparent molar enthalpy spheric pressure has already been experimentally deter-
fL3(T , x1?, m ) of CaCl2 in the ternary system, that mined by Vercher, Muñoz and Martinez-Andreu (1991)
remains valid in the temperature and salt concentration for that system, the availability of correlations for its
ranges encountered in the simulation of the column, and calorimetric properties would at last render possible the
makes unnecessary the replacement of the relative simulation of the original process described by Gorhan
apparent molar enthalpy fL3(T , x1?, m ) for CaCl2 in (1932a,b) in his patents.
the binary mixture ethanol/water by fL (T , m ), which is
actually meant for CaCl2 in aqueous solution. In this
way, it would be possible to simulate more accurately
Acknowledgements
the energy balances of the column and, in consequence,
to obtain a better estimate of the reboiler heat duty, Financial support from the School of Chemical
which is the crucial factor that makes saline extractive Engineering, Universidad del Valle, Colombia, is grate-
distillation a competitive alternative for the industrial fully acknowledged by the authors.
production of absolute ethanol. Third, the VLE mea-
surements made by Nishi (1975) for the ethanol/water/
calcium chloride system, could be extended to other salt
concentrations to explore more thoroughly the capabil- Appendix A
ity of CaCl2 to break the ethanol /water azeotrope.
The mathematical model proposed in this work for For the NRTL-E model, the expression for the
simulating saline extractive distillation columns is suffi- activity coefficient of a solvent species m in a mixed
ciently general to be applied to other mixed solvent/salt solvent/salt system was originally given by Chen and
systems, provided that enough experimental data be- Evans (1986) in the generalized format:
X s4 Xa Gam2 tam2 Xc Gcm2 tcm2 Xm1 Gm1 m2 tm1 m2

Xj Gjm tjm
X X G
j
ln gm X Xm? mm? Xm2 Gm2 m2 tm2 m2 (A7)
Xk Gkm m? Xk Gkm? s5 Xa Gac;ac Xc Gcc;ac Xm1 Gm1 c;ac Xm2 Gm2 c;ac (A8)

k
X
k
s6 Xa Gac;ac tac;ac Xc Gcc;ac tcc;ac Xm1 Gm1 c;ca tm1 c;ac
Xk Gkm? tkm? Xm2 Gm2 c;ac tm2 c;ac (A9)
XX X
kX X a?
tmm? s7 Xa Gaa;ca Xc Gca;ca Xm1 Gm1 a;ca Xm2 Gm2 a;ca (A10)
Xk Gkm? c a? Xaƒ
s8 Xa Gaa;ca taa;ca Xc Gca;ca tca;ca Xm1 Gm1 a;ca tm1 a;ca

k aƒ
X Xm2 Gm2 a;ca tm2 a;ca (A11)

Xk Gkc;a?c tkc;a?c
XG The definitions for G and t , and the symmetry
X c mc;a?c tmc;a?c kX
Xk Gkc;a?c Xk Gkc;a?c condition for the non-randomness factor a given by
k k Chen and Evans (1986), yield the following relations:
XX X XG Gm1 ;m2 exp(am1 ;m2 tm1 ;m2 ) (A12)
X c? X a ma;c?a
Xcƒ Xk Gka;c?a Gm2 ;m1 exp(am1 ;m2 tm2 ;m1 ) (A13)
a c?
cƒ
X
k
tm1 m1 tm2 m2 tac;ac tca;ca 0
Gm1 m1 Gm2 m2 Gac;ac Gca;ca 1
(A14)
(A15)
Xk Gka;c?a tka;c?a
kX
tma;c?a (A1) The assumption of like-ion repulsion (no ions of like
Xk Gka;c?a charge exist near each other) made by Chen and Evans
k
(1986) to derive the NRTL-E model can be used to show
where subscripts k and j refer to any species (solvent or that:
ionic), subscripts a , a?, a ƒ refer to the anions, and Gcc;ac Gaa;ca 0 (A16)
subscripts c , c?, cƒ refer to the cations. For the ethanol/ Gcc;ac tcc;ac Gaa;ca taa;ca 0 (A17)
water/CaCl2 system, there are four species in solution:
ethanol, water, Ca 2 ions, and Cl 1 ions. For the sake Also, the definitions given by Chen and Evans (1986)
of clarity and for the purpose of making the results of for amc,ac , ama,ca tmc ,ac and tma,ca together with the
this work entirely reproducible, Eq. (A1) is expanded symmetry condition for a , yield the following relations
out in the following way to obtain explicit expressions of equivalency (with m standing for either solvent 1 or
for the activity coefficients of ethanol (solvent m1) and 2):
water (solvent m2): aam acm aca;m (A18)

s 2 X m1 G m1 m 1 s2 X G tam tcm tca;m (A19)
ln gm1 t m1 m1 m2 m1 m2
s1 s1 s1 s3 Gam Gcm Gca;m exp(aca;m tca;m ) (A20)
amc;ac ama;ca am;ca aca;m (A21)
s XG s
tm1 m2 4 c m1 ;ca tm1 ;ca 6 tmc;ac tma;ca tm;ca (A22)
s3 s5 s5
Gmc;ac Gma;ca Gm;ca exp(aca;m tm;ca ) (A23)
XG s
a m1 ;ca tm1 ;ca 8 (A2) Substitution of Eqs. (A12), (A13), (A14), (A15),
s7 s7
(A16), (A17), (A18), (A19), (A20), (A21), (A22) and
s X G s X G (A23) into Eqs. (A4), (A5), (A6), (A7), (A8), (A9), (A10)
ln gm2 4 m1 m2 m1 tm2 m1 2 m2 m2 m2
s3 s1 s1 s3 and (A11) shows that the NRTL-E model for the
ternary system ethanol (m1)/water (m2)/CaCl2 (ca),
s XG s
tm2 m2 4 c m2 ;ca tm2 ;ca 6 requires the values for nine temperature-independent
s3 s5 s5 parameters:

XG s am1 ;m2 ; tm1 ;m2 ; tm2 ;m1 ; aca;m1 ; tca;m1 ; tm1 ;ca ; aca;m2 ; tca;m2 ; tm2 ;ca
a m2 ;ca tm2 ;ca 8 (A3)
s7 s7 (A24)
where The effective local mole fraction Xj /Cj xj ,tr of ionic

species j , is defined by Chen and Evans (1986) as the
s1 Xa Gam1 Xc Gcm1 Xm1 Gm1 m1 Xm2 Gm2 m1 (A4) product of the true liquid phase mole fraction xj ,tr and
s2 Xa Gam1 tam1 Xc Gcm1 tcm1 Xm1 Gm1 m1 tm1 m1 the absolute value of the ionic valence number Cj . For
Xm2 Gm2 m1 tm2 m1 (A5) the solvent molecules, Xj is identical to xj,tr. The true
mole fractions are associated with the quaternary system
s3 Xa Gam2 Xc Gcm2 Xm1 Gm1 m2 Xm2 Gm2 m2 (A6) consisting of molecules of ethanol (1) and water (2),
Ca 2 ions (c), and Cl 1 ions (a ), and can therefore, be H n1 h1

f H2 (B1)
related to the apparent (or stoichiometric) mole frac- n2
tions xj , for the ternary system ethanol (1)/water (2)/
non-dissociated CaCl2 (3) through the following expres- where H is the enthalpy of the mixture, h1 is the molar
sions: enthalpy of pure solvent, n1 is the solvent mole number,
and n2 is the solute mole number. From the summability
x1 relation for partial molar properties, H is given by:
x1;tr (A25)
2x3 1
H n1 h̄1 n2 h̄2 (B2)
x2
x2;tr (A26) where h̄1 and h̄2 are the solvent and solute partial molar
2x3 1
enthalpies, respectively. At infinite dilution of the solute
x3 in the solvent, the partial molar value of the solvent
xc;tr (A27)
2x3 1 enthalpy h̄1 equals the pure component value h1.
2x3 Consideration of this limiting condition and substitution
xa;tr (A28) of Eq. (B2) into Eq. (B1) yields:
2x3 1
fH2 lim fH2 lim h̄2 h̄2 (B3)
In turn, the apparent mole fractions x1, x2, x3 are n2 00 n2 00
related to the mole fractions on a salt-free basis x1?, x2?,
x3? as follows: Combination of Eqs. (B1), (B2) and (B3) gives:
x?3 n2 fH2 n2 fH2 n1 (h̄1 h1 )n2 (h̄2 h̄2 ) (B4)
x3 (A29)
1 x?3 If the state of pure component and the state at infinite
x1 x?1 (1x3 ) (A30) dilution are (temporarily) defined as the reference states
x2 x?2 (1x3 ) (A31) for the solvent and the solute, respectively, then the
expressions h̄1 0 h1 and h̄2 0 h̄2 may be substituted
Nishi (1975) measured the VLE for the ethanol (1)/ into Eq. (B4) to yield:
water (2)/CaCl2 (3) system, at a fixed salt concentration
of 16.7 wt.% on a salt-free basis, and reported the values n2 fH2 n2 fH2 n1 (h̄1 h̄1 0 )n2 (h̄2 h̄2 0 )
for the vapor phase mole fraction of ethanol y1 and the
boiling temperature T corresponding to 12 values for n1 l¯1 n2 l¯2
the liquid phase salt-free mole fraction x1?. The salt
concentration fixed for the measurement yields the L (B5)
following expression for x3?: where l¯1 and l¯2 are the solvent and solute relative partial
(2) molar enthalpies, respectively, and L is the relative
0:167Mw
x?3 (A32) enthalpy of the mixture.
Mw;3
The relative apparent molar enthalpy of the solute is
where Mw,3 /110.986 g/mol is the molecular weight of defined as:
CaCl2, and M(2)
w is the molecular weight of the binary
solvent mixture, which in terms of the molecular weights L n1 l1
fL 2 (B6)
of the two solvents Mw,1 /46.06952 and Mw,2 / n2
18.01534 g/mol, is given by:
Due to the choice of reference state for the solvent,
Mw (2) x?1 Mw;1 x?2 Mw;2 (A33) l1 /h1/h01 /0. Substitution of this result into Eq. (B6)
and comparison of Eqs. (B5) and (B6) gives:
Eqs. (A29), (A32) and (A33) may be used to compute
the salt molality in the ternary system, as shown in fL2 fH2 fH2 (B7)
Appendix C. The apparent mole fractions x1, x2, x3 are
The main lines of the derivation leading to Eq. (B7)
involved in the calculation of VLE ratios as explained in
can be found in the classic textbook by Klotz and
Section 3.
Rosenberg (1972).
Let us consider now the process of dissolution of n2
moles of solute into n1 moles of solvent. The enthalpy
change for this process is known as integral heat of
Appendix B solution and is given by:
DHsol i n1 (h̄1 h1 )n2 (h̄2 h2 ) (B8)
Let us consider a mixture of a solvent (component 1)
and a solute (component 2). The apparent molar The molar integral heat of solution is the enthalpy
enthalpy of the solute is defined as: change based on 1 mol of solute:
DHsol i H n1 h 1 T
Dhsol i h2
n2 n2
idg
h (T)
gc
T0
p
idg
(T)dT (C3)
fH2 h2 (B9)

The correlation by Aly and Lee (1981) for the ideal
Eq. (B1) was used for writing Eq. (B9). Combination gas molar isobaric heat capacity given as
of Eqs. (B7) and (B9) and use of Eq. (B3) yields:
C=T E=T
Dhsol i fL2 (h̄2 h2 ) (B10) cp idg AB 2
D 2
(C4)
sinh(C=T) cosh(E=T)
By considering the process of dissolution of the solute
was used to compute the integral in Eq. (C3), yielding
in an infinite amount of the solvent, the corresponding
the expression:
change of enthalpy may be written as:
Dhsol i; h̄2 h2 (B11) hidg (T)hidg (T0 )A(T T0 )

Substitution of Eq. (B11) into Eq. (B10) finally yields: C C
BC coth coth
T T0
Dhsol i fL2 Dhsol i; (B12)

E E
Eqs. (B11) and (B12) may be extended to the ternary DE tanh tanh (C5)
system solvent (1)/solvent (2)/salt (3) to be used for the T T0
derivation of the liquid phase enthalpy model for mixed To compute the ideal gas molar enthalpy in J/kmol
solvent/salt systems presented in Section 4. with T in K, values for the constants A , B , C , D and E
were taken from a pure component database made
available to users of the CHEMSEP package (Kooijman et
Appendix C al., 1993). For ethanol, A /4.39 /104, B /1.463 /105,
C /1.404 /103, D /7.82 /104, E/6.135 /102. For
water, A /3.3363 /104, B /2.679 /104, C /2.6105 /
C.1. Vapor pressures 103, D /8.896 /103, E /1.169 /103.
The vapor pressure was calculated by use of the

extended Clausius /Clapeyron equation: C.3. Pure component liquid phase enthalpies
B
ln Psat A C ln T DT E (C1) The liquid phase molar enthalpies of the pure
T
components h1 and h2 required for the application of
where T is the absolute temperature. For Psat in kPa and Eq. (39), were obtained by subtracting the correspond-
T in K, values for the constants A , B , C , D and E were ing molar heats of vaporization from the ideal gas molar
taken from a pure component database made available enthalpies given by Eq. (C5):
to users of the CHEMSEP package (Kooijman, Haket &
Taylor, 1993). For ethanol, A /74.475, B//7164.3, hk (T) hk idg (T)Dhk vap (T) (C6)
C //7.327, D /3.134 /106, E /2. For water, A / The molar heat of vaporization was computed by use
73.649, B //7258.2, C //7.3037, D /4.1653 /106, of the following correlation:
E /2.
Dhvap A(1Tr )F (C7)
C.2. Vapor phase enthalpies where

F BCTr DTr 2 ETr 3 (C8)
The molar enthalpy of the vapor phase hV was
calculated from the ideal gas mixture contribution, Tr /T /Tc is the reduced temperature and Tc is the
critical temperature. To compute the molar enthalpy of
hV y1 h1 idg y2 h2 idg (C2)
vaporization in J/kmol with T in K, values for the
by neglecting the residual enthalpies of the mixture constants A , B , C , D , E and the critical temperature
because of the low pressure (1 atm) level chosen for the were taken from a pure component database made
simulation of the column. The ideal gas molar enthalpy available to users of the CHEMSEP package (Kooijman et
hidg was obtained by analytically integrating the ideal al., 1993). For ethanol, A /5.69 /107, B /0.3359, C /
gas molar isobaric heat capacity from the reference 0, D /0, E /0, Tc /516.25 K. For water, A /5.2053 /
temperature T0 /298.15 K (at which hidg is taken to be 107, B /0.3199, C //0.212, D /0.25795, E /0, Tc /
zero), to the temperature of interest T , as follows: 647.13 K.
2
C.4. Heat of mixing for the solvent mixture 1 2pNA rw 1=2 e 3=2
Af (C13)
3 1000 o w kB T
The molar heat of mixing for the ethanol (1)/water (2) (0)
L @bMX @bMX (1) 2
liquid mixture was computed by use of the following BMX
correlation obtained by Larkin (1975): @T @T xMX 2
[1(1xMX )exp(xMX )] (C14)
1=2
E
h x?2 (1x?2 ) xMX aI (C15)
(0)
fA(1x?2 )1=2 @bMX q2 q3
q4 2q5 T (C16)
@T T2 T
BC(1x?2 )D(1x?2 )2 E(1x?2 )4 g (C9)
@bMX (1) q
7 q9 2q10 T (C17)
where x2? is the liquid phase mole fraction of water on a @T T2
salt-free basis. q12 q13
To compute the molar heat of mixing in J/mol, values CMX L q14 2q15 T (C18)
T2 T
for the constants A , B, C , D , E were computed from a
quadratic correlation in terms of the absolute tempera- q17 q18
DMX L q19 2q20 T (C19)
ture given by Larkin (1975). Those values have also been T2 T
reported in the heat of mixing compilation published by q22 q23
Christensen, Hanks and Izatt (1982). For the range of EMX L q24 2q25 T (C20)
boiling temperatures in the distillation column, values of T2 T
the constants are: A //7141.69, B /16 904.9, C // q27 q28
FMX L q29 2q30 T (C21)
16 370.9, D /9138.04, E //2535.6 at 70 8C; A // T2 T
3256, B /10 202.5, C //8892.13, D /4086.53, E //
1117.92 at 90 8C; A //1232.4, B /8597.94, C // In Eq. (C10), b /1.2, and a /2 in Eq. (C15). The
9503.59, D /5425.97, E //1325.26 at 110 8C. Based quantities AH and Af given by Eqs. (C12) and (C13) are
on the values of the heat of mixing at these three Pitzer /Debye /Hückel limiting slopes defined in an
temperatures, a quadratic interpolation (Burden & earlier paper by Ananthaswamy and Atkinson (1984),
Faires, 1993) was performed to compute values of that with NA /6.022045/1023 as Avogadro’s number, e/
quantity at other temperatures. 4.803242 /10 10 esu as the charge of electron, kB /
1.38066 /1016 erg/K as Boltzmann’s constant, and
C.5. Relative apparent molar enthalpy of solute R /8.31441 J/mol K.
In Eqs. (C10) and (C15), I is the ionic strength of the
As explained in Section 4, for the implementation of solution defined as
the column model, it was decided to replace the relative
1X
nions
apparent molar enthalpy fL3(T , x1?, m ), for CaCl2 in the I m i zi 2 (C22)
binary mixture ethanol/water, by fL (T , m ) for CaCl2 in 2 i1
aqueous solution, computing fL (T , m ) at the salt where nions is the number of ion classes, mi is the
molality m of the ternary mixture. The latter quantity molality and zi the valence number of the ions of class i.
(in kJ/mol) was computed by use of the following For CaCl2, there are only two classes of ions, Ca 2 and
correlation obtained by Ananthaswamy and Atkinson Cl 1; therefore, according to the stoichiometry for the
(1985): dissociation of this salt, I /3m , where m is the salt

1 molality, which is given by the following defining
fL (nM nX )½ZM ZX ½AH ln(1bI 1=2 ) expression:
2b
3
(nM nX )RT 2 mG (C10) 10 x3
m (C23)
Mw (2) 1 x3
where
2 1 where x3 is the apparent (or stoichiometric) mole
G 2BMX L (nM nX )1=2 mCMX L (nM nX )m2 DMX L fraction of the salt in the ternary system as given by
3 2
Eqs. (A29) and (A32) and M(2) w is the molecular weight
2 of the binary solvent mixture as defined by Eq. (A33).
(nM nX )3=2 m3 EMX L (nM nX )2 m4 FMX L (C11)
5 Also, in this case, the stoichiometric numbers are
nM /1 and nX /2 and and the charge numbers are
2 1 @ ln o w 1 @ ln rw
AH 6RT Af (C12) ZM //2 and Zx //1. For the sake of completeness,
T @T 3 @T values for the coefficients qk are listed in Table 5.
Table 5 where P is the pressure in bar. The parameters B , C and

Coefficient values given by Ananthaswamy and Atkinson (1985) for D are obtained from the following expressions in terms
their correlations for the relative apparent molar enthalpy fL and the
of the absolute temperature T (in K):
partial molar isobaric heat capacity c̄p of CaCl2 in aqueous solution
q2 5107.78
D u1 exp(u2 T u3 T 2 ) (C27)
q3 46.4785 u5
q4 /0.138971 C u4 (C28)
q5 6.82557/10 5 u6 T
q7 /498.241 u8
q9 /1.64685/10 2 B u7 u9 T (C29)
q10 2.34630/10 5 T
q12 /9676.33
q13 /84.8338 Values for the constants are as follows: u1 /342.79,
q14 0.246219 u2 //5.0866 /10 3, u3 /9.4690 /107, u4 //
q15 /1.18352/10 4 2.0525, u5 /3115.9, u6 //182.89, u7 //8032.5, u8 /
q17 3836.10
4.2142 /106, u9 /2.1417.
q18 33.9226
q19 /9.95956/10 2 The dielectric constant temperature derivative re-
q20 4.84995/10 5 quired for Eq. (C12) is obtained analytically from Eqs.
q22 /565.554 (C26), (C27), (C28) and (C29):
q23 /5.04325
q24 1.49455/10 2 do w dD dC BP C(103 P)
q25 /7.35441/10 6 ln
dt dt dt b 103 (B P)(B 103 )
q27 27.6926
q28 0.248007
dB
q29 /7.38508/10 4 (C30)
q30 3.65452/10 7 dt
q31 /275.690
q32 2.73117 where
q33 /4.99191/ 2
q34 1.65270/10 4 dD
D(u2 2u3 T) (C31)
dt
dC u5
In Eq. (C13), rw is the mass density of water (in g/ (C32)
dt (u6 T)2
cm3). Ananthaswamy and Atkinson (1984) used the
following correlation by Kell (1975): dB u
8 u9 (C33)
dt T2
a a1 t a2 t2 a3 t3 a4 t4 a5 t5
rw 0 (C24)
1 a6 t
For rw in kg/m3 and the temperature t in 8C, values

for the constants in Eq. (C24) are as follows: a0 /
999.83952, a1 /16.945176, a2 //7.9870401/103, C.6. Partial molar isobaric heat capacity of solute at
a3 //46.170461 /106, a4 /105.56302 /109, a5 / infinite dilution
/280.54253 /10 12, a6 /16.879850 /103.
The mass density temperature derivative required for As explained in Section 4, for the implementation of
Eq. (C12) is obtained analytically from Eq. (C24): the column model, it was decided to replace the partial
molar isobaric heat capacity of solute at infinite dilution
d ln rw a1 2a2 t 3a3 t2 4a4 t3 5a5 t5 c̄p;3 /(T , x1?) for CaCl2 in the binary ethanol/water

dt a0 a1 t a2 t2 a3 t3 a4 t4 a5 t5 mixture, by c̄p /(T ) for CaCl2 in aqueous solution. The
latter quantity was computed by use of the following
a6 correlation by Ananthaswamy and Atkinson (1985):
(C25)
1 a6 t
c̄p q31 q32 (T T0 )q33 (T T0 )2
In Eq. (C13), o w is the dielectric constant of water
q34 (T T0 )3 (C34)
(dimensionless). Ananthaswamy and Atkinson (1984)
used the following correlation by Bradley and Pitzer where c̄p is given in J/mol K, T is in K, and T0 /
(1979): 298.15 K. Values for the coefficients q31 to q34 are listed
in Table 5.
BP
o w DC ln (C26) The integral (in J/mol) required for Eq. (38) is
B 103 obtained analytically from Eq. (C34):
T Burden, R. L., & Faires, J. D. (1993). Numerical analysis (5th ed.).

1
g c̄
T0
p

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2
q32 (T T0 ) 2 PWS Publishing Company.
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Modeling and Simulation of Saline Extractive Distillation Columns For The Production of Absolute Ethanol

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Computers and Chemical Engineering 27 (2003) 527 /549

Modeling and simulation of saline extractive distillation columns for

1. Introduction registered by Adolf Gorhan in the period 1932/1934

stream, for the reflux ratio, and for the number of

Fig. 2. General saline extractive distillation stage.

5) Energy balance around stage j:

All the feed-stream flow rates Fj , the liquid Uj and

1) Overall material balance discrepancy function at

5) Energy balance discrepancy function at stage j :

x1? y1 (experimental) y1 (calculated) Dy1 T (experimental) (8C) T (calculated) (8C) DT (8C)

0.000 0.000 0.000 0.000 102.80 103.69 0.89

Substitution of Eq. (27) into Eq. (30) and use of the

performed starting from an initial solution with a salt ?

to compute VLE ratios, were obtained from the experi- Table 2

Stage T (8C) V (kmol/h) y1 y2 L (kmol/h) x1 x2 x3 m (mol/kg)

1 78.31 0 0 0 120.00 0.99998 0.00002 0 0

Mole fractions are numbered as ethanol (1)/water (2)/CaCl2 (3).

1 /35031 0.0 /35031 11789 /91447 /13003 0 /35031

X s4  Xa Gam2 tam2 Xc Gcm2 tcm2 Xm1 Gm1 m2 tm1 m2

X Xm2 Gm2 a;ca tm2 a;ca (A11)

where The effective local mole fraction Xj /Cj xj ,tr of ionic

Ca 2 ions (c), and Cl 1 ions (a ), and can therefore, be H  n1 h1

 fH2 h2 (B9)

The vapor pressure was calculated by use of the

C.2. Vapor phase enthalpies where

Table 5 where P is the pressure in bar. The parameters B , C and

For rw in kg/m3 and the temperature t in 8C, values

T Burden, R. L., & Faires, J. D. (1993). Numerical analysis (5th ed.).

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1 /35031 0.0 /35031 11789 /91447 /13003 0 /35031

X s4 Xa Gam2 tam2 Xc Gcm2 tcm2 Xm1 Gm1 m2 tm1 m2

where The effective local mole fraction Xj /Cj xj ,tr of ionic

Ca 2 ions (c), and Cl 1 ions (a ), and can therefore, be H n1 h1

fH2 h2 (B9)