189

A Computational
Condensation

Design Method for Multicomponent

Eine Methode zur Berechnung der Kondensation

ANDRZEJ
Polish

BURGHARDT

Academy

(Received

of Sciences,

and MAREK
Institute

von Vielstoffgemischen

BEREZOWSKI

of Chemical

Engineering,

Bdtycka

5, 44-100

Gliwice

(Poland)

June 30, 1988)

Abstract
A mathematical
model has been developed which describes quantitatively
the phenomena
occurring during the
condensation
of multicomponent
mixtures in which all constituents
condense to form a homogeneous
liquid
phase. As a result of the analysis of the model equations two specific modes of the vapour mixture condensation
have been defined and described: equilibrium
condensation
and total local condensation.
The derived model of the process and the results of the analysis of the model equations have served as a basis
for the proposed method of condenser design as well as for the relevant algorithm and numerical calculation
procedure. The proposed numerical algorithm for the condenser design was tested for three- and tive-component mixtures. By changing the composition
and the inlet temperature
of the vapour, as well as the temperature
of the cooling medium, a wide range of condensation
intensities
was covered, and thus the stability and
convergence
of the numerical method were tested.
The results of the theoretical analysis as well as those of the numerical calculations
led to the development
of a simplified method of calculation which is particularly useful for mixtures with more than three components,
and has the advantage of being almost five times faster.

Kurzfassung
Ein mathematisches
Model1 wurde entwickelt, das den Vorgang der Kondensation
eines Vielstoffgemisches,
dessen Komponenten
alle kondensierbar
und dessen Kondensat eine homogene fliissige Phase bildet, quantitativ
beschreibt. Als Ergebnis der Analyse der Modellgleichungen
lie&n sich zwei Grenzfalle der Kondensation
eines
Vielstoffgemisches
definieren und beschreiben:
die Gleichgewichtskondensation
und die lokale Totalkondensation.
Dieses Model1 bildet die Grundlage
fiir den Vorschlag zu einer Berechnungsmethode
fur die Auslegung von
Kondensatoren
fur Vielstoffgemische.
Beispielhaft wird der Berechnungsalgorithmus
an einem Drei- und einem
Fiinfstoffgemisch
erhiutert.
Die Parameter
Eintrittszusammensetzung,
Temperatur
des Dampfes
und
Eintrittstemperatur
des Kiihlmittels
wurden in breiter Variation untersucht,
urn damit von der Gleichgewichtskondensation
bis zur lokalen Totalkondensation
die Stabilitlit und die Konvergenz
des Berechnungsverfahrens
zu priifen.
Aufgrund der theoretischen
Analyse und der numerischen
Berechnungen
konnte ein einfaches Ngherungsverfahren entwickelt werden, da13 besonders ntitzlich bei Vielstoffgemischen
mit mehr als drei Komponenten
ist.
Die Rechenzeiten
des Naherungsverfahrens
sind nur ein funftel derer der vollstandigen
Methoden.

Wnopse
Ein mathematisches
ModeN wurde entwickelt,
das
die Kondensation
eines Vielstoffgemisches
quantitativ
beschreibt,
dessert Komponenten
alle kondensierbar
sind und dessen Kondensat
eine homogene Jliissige
Phase bildet. Dieses Modell
ist die Grundlage
der
vorgeschlagenen
Methode zur Auslegung entsprechen der Kondensatoren.

0255-2701/88/%3.50

Chem.

Eng.

Process..

24 ( 1988)

Die Veriinderung
der Stoflstriime
beider Phasen,
deren Zusammensetzung
und Temperatur
im Verlauf
der Kondensation
wird durch ein System von differentiellen Massen- und Enthatpiebilanzen
wiedergegeben.
Urn die in diesen Bilanzen
auftretenden
Stoffstromdichten
der von der Dampf- in die Fbissigkeitsphase iibergehenden
Komponenten
und die Wiirmestromdichte
durch den Kondensatfilm
berechnen
zu
kiinnen, ist die Kenntnis
der an der Phasengrenze

189-202

Elsevier

Sequoia/Printed

in The

Netherlands

190

herrschenden
Bedingungen
erforderlich.
Die Zustandsvariablen
(Zusammensetzung
der Dampf- und
der Fliissigkeitsphase,
Temperatur an der Phasengrenze) lassen sich mit den Gln. (I)+)
aufgrund eines
Systems algebra&her
Verkniipfungen berechnen. Die
Stoffstromdichten
der Komponenten
von Vielstoffgemischen sind durch die Gln. (6)-o-() definiert.
Der an der Phasengrenze angenommene Gleichgewichtszustand wird durch die Matrixrelationen
(13)
und (14) beschrieben. Nach Einftihrung oben genannter
Abhiingigkeiten in die Gl. (I) erhalten wir die Matrixformel (15), aufgrund derer die Molenbrtiche der Komponenten an der Phasengrenze
bestimmt
werden
konnen.
Die Matrizen der Stofltibergangskoefizienten
und
der Korrekturkoefizienten
fur Vielstoffgemische sind
durch die Gln. (16)-(23) gegeben. Bei Einsetzen der
Gln. (16)-(18) in der Beziehung (IS) gelangt man nach
Transformationen zur Gl. (28). Aus dieser Gleichung
geht hervor, da@ die Zusammensetzung
der friissigen
Phase an der Phasengrenze stark von der Kondensationsintensittit abhiingt, die durch die globale Molenstromdichte
N charakterisiert
ist, welche in den
Matrizen 8 und 4 vorkommt. Es wurde die Veriinderung von x, als Funktion von 4 analysiert, und es
wurden zwei Grenzftille des Kondensationsmechanismus fir 4 -B 0 und 4 --t co herausgestellt. Aus der Gl.
(28) geht hervor, da@ im Falle sehr groper Molenstromdichten
des kondensierenden Dampfes N + co
die Zusammensetzung
der Fhissigkeit an der Phasengrenze xi, gleich der Dampfzusammensetzung
yi ist. In
diesem Fall ist die Temperatur der Phasengrenze, die
aus den Gleichgewichtsbeziehungen
hervorgeht, gleich
der Siedetemperatur
der Fliissigkeit von der Zusammensetzung
x,, = yi. Den KondensationsprozeB
bei
groaen Molenstromdichten
N bezeichnet man als artlithe Totalkondensation.
Im zweiten Grenzfall, das he@ fur N + 0, gelten
die Gln. (33) und (34), die die sog. Gleichgewichtskondensation de@ieren. Fur die Werte von N, die von
Null und Unendlich abweichen, ist das Interval1 der
Phasengrenztemperaturen
durch die Ungleichung (35)
bestimmt.
Die Abhtingigkeit (28) kann erheblich vereinfacht
we&en durch Einfiihrung der Annahmen (36) und (37),
die den Stofltransport
im Kondensatjilm
charakterisieren. Die Anwendung der Filmtheorie fur die Bestimmung a& Matrix der Korrekturkoefizienten
(20)
fiihrt zum System der algebraischen Gleichungen (39)
(41), aufgrund deren die Zustandsvariablen
an der
Phasengrenze
und die globale
Molenstromdichte
berechnet werden kiinnen.
Die quantitative Formulierung des Modells, die die
Berechnung der Veranderungen der Zustandrvariablen
in der Dampfphase
und im Kondensat erlaubt, ist
durch a& System der Dtzerentialgleichungen
(43)(46) gegeben. In detaillierten Berechnungen ist es niitzlich, den Kondensationsgrad
(47) einzuftihren und das
oben genannte System der Dtrerentialgleichungen
in
die Gln. (48)-(50) zu transformieren. Die Stoflstriime
der beiden Phasen und die Zusammensetzung der piis-

sigen Phase kiinnen aus den Gln. (51)-(53) berechnet

wet&n,
Urn die Wiirmeaustauschflache
aufgrund der Gl.
(54) bestimmen zu kiinnen, miissen die Dtrerentialgleichungen (48H50) im Bereich des Kondensationsgrades &I fiir gegebene Randbedingungen integriert
wetden. Dieses Dtrerentialgleichungensystem
wurde
mit Hiife der modtj?zierten Methode von Euler integriert. Die erhaltenen Rekursionsgleichungen (58x65)
&finieren direkt die Zustandsvariablen
(yi, xi, T,,
T,, GG, G3 am Ende jedes lntegrationsschrittes.
Die
Genauigkeit dieser Methode ist vergleichbar mit der
der Runge-Kutta-Gill
Methode vierter Ordnung, die
lntegrationszeit ist aber vie1 kiirzer.
Die Zustandrvariablen an der Phasengrenze, die bei
jedem lntegrationsschritt bendtigt wet-den, wurden aus
den Gln. (39x41)
mit Hilfe der Newton-Raphson
Methode berechnet. Die Eigenwerte der Matrix der
D#usionskoeflzienten
(68) und (69), die zur Berechnung der Matrixfunktion exp( -4&
notig sind, wurden mit HiIfe der Transformationsmethode,
die in Lit.
I4 bearbeitet wurde, berechnet.
Der vorgeschlagene Berechnungsalgorithmus
zum
Entwurf
von Kondensatoren
wurde anhand von
Berechnungen
eines Dreistoffund eines Fiinfstoffgemisches
erliiutert. Die Eintrittszusammensetzungen und Temperaturen
des Dreistoflgembches
Benzol-Toluol-Xylol
wie such die Eintrittstemperaturen des Kiihlmittels sind in der Tabelle I angegeben.
GroJe Anderungen der oben genannten Parameter
wurden vorgenommen, urn einen breiten Bereich &r
Kondensationsintensitiiten
zu analysieren
(von der
Gleichgewichtskondensation
bis zur Sirtlichen Totalkomiensation) und urn auf diese Weise die Stabilitiit
und Konvergenz der Methode zu priifen.
Es hat sich gezeigt, da4 in alien in &r Tabelle 1
zusammengestellten Berechnungsbeispielen die Berechnungsprozedur konvergent und stabil war, sogar ftir
Kondensationsstromdichten,
die gegen Null gehen
(N + 0). In den Bildern 2-6 sind die Zusammensetzungs- und TemperaturproJle als Funktionen des Kondensationsgrades fiir zwei gewiihlte Temperaturen des
Kiihlmittels dargestellt.
Die Ergebnisse der Berechnungen fiir ah F&fstoflgemisch, dessen Eintrittszusammensetzung
in &r
Tabelle 2 gegeben ist, wurden in den Bildern 7-9
dargestellt.
Die wachsende Zahl der Komponenten verliingert
erheblich die Zeit der numerischen Berechnungen. Das
wird dadurch verursacht, a?$ in jedem Integrationsschritt die Eigenwerte der Diffusionskoefizientenmatrix
berechnet werden mtissen. Dies ist die zeitraubendste
numerische Prozedur des ganzen Algorithmus. Deshalb
wurde eine vereinfachte Methode zur Auslegung von
Kondensatoren fiir Vielstofigemische
vorgeschlagen.
Da ftir die Mehrzahl der Vielstoflgemische die Dt#iisionskoeflzientenmatrix
eine diagonal-dominierend
Matrix
ist, wurden die nichtdiagonalen
Elemente
dieser Matrix vernachliissigt. Auf diese Weise werden
die Kreuzeflekte des Stofltransportes
vernachllissigt,
und die Eigenwerte mu&en nicht berechnet werden.

191
Bei dieser Methode wird die Berechnungszeit ungeftihr
auf ein Funftel reduziert.
Ein Vergleich der Ergebnisse, die mit Hilfe dieser
Methode erhalten wurden, mit den Ergebnissen der
genauen Berechnungen ist in den Bildern IO und 11
dargestelit. Darin zeigt sich, daJ3 diese Methode zur
niiherungsweisen Auslegung von Kondensatoren fiir
Vielstofiemische
empfohlen werden kann.

1. Introduction
The methods currently used in the design of heat
exchangers in which multicomponent
condensation
takes place fall into two groups: the equilibrium
methods employing the works of Kern [ 11, Silver [2]
and Bell and Chaly [3], and those based on the
original paper by Colbum and Drew [4]. To describe
the phenomena
occurring during the condensation,
the latter group makes use of the relations defining
the mass and energy fluxes both in the vapour phase
and in the layer of condensate.
The discussion carried out in ref. 5 shows that the use of the equilibrium methods in the design of condensers
may
lead to substantial
errors incurred in determining
the
heat fluxes and, consequently,
to incorrect dimensions of these apparatuses.
Although
there are a number of papers dealing
with the condensation
of multicomponent
mixtures
containing
inert components
[6-lo], the condensation of mixtures
in which all constituent
species
condense has not been properly analysed. The extensive study presented in ref. 5 is restricted to binary
mixtures.
The literature survey carried out in ref. 5 reveals
that previous research, both experimental
and theoretical, was concerned
exclusively with binary mixtures. Moreover, the authors were interested mainly
in determining
the overall coefficients of heat transfer
from the condensing vapour to the wall, based on the
measured heat fluxes and assuming various empirical
values of the driving force. Thus, a real mechanism
of the process, which also includes the diffusion of
the condensing
species, was not considered.
The reason for the apparent lack of interest in the
process discussed lies in the considerable
mathematical difficulties concerned with the design procedures
for such condensers.
While, by employing
certain
simplifying assumptions,
there is always a possibility
of obtaining explicit relations defining the individual
mass fluxes for mixtures containing inert components
[ 11, 121, the fluxes for mixtures in which all species
condense are given by implicit formulae.
It should also be noted that the evaluation
of the
state variables at the vapour-liquid
interface along
the condenser becomes much more complicated
than
in the case of mixtures with some inert components.
This has also been pointed out in ref. 5, where a
specially developed
procedure
for determining
the
interfacial state variables was presented.
The main objective of the present paper is to
derive a mathematical
model describing
quantita-

tively the phenomena

occurring during the condensation of multicomponent
mixtures in which all constituents condense, employing both the conclusions
given in ref. 5 and the existing experimental
results
for binary mixtures.
The model will serve as a basis for developing an
appropriate
numerical design procedure.

2. The model

and its analysis

The basic assumptions

of the model of condensation of vapour mixtures are as follows.
(1) The layer of condensate
flows down the wall
as a laminar film, and the flow itself is determined by
the equilibrium
between the gravitational
and viscous forces. The possible effect of turbulence
of the
layer of condensate
and that of the vapour velocity
on the heat transfer resistance may be allowed for
using relations valid for the condensation
of pure
substances.
(2) The flow of the vapour phase is a plug flow
with perfect radial mixing.
(3) According to the film theory, the diffusional
and heat resistances
are located in suitably
thin
layers adjacent to the interface and are defined by the
mass and heat transfer coefficients.
(4) Thermodynamic
equilibrium
prevails at the
interface.
(5) The wall is cooled from the outside by an
appropriate
coolant which takes away the heat of
condensation.
(6) The possibility of the formation of mist in the
vapour phase is not allowed for. It is also assumed
that the temperature
of the vapour is determined
solely by the equilibrium
relations from the moment
when it reaches the dew point temperature.
Typical concentration
and temperature
profiles
are given in Fig. 1, together with the positive directions of the mass and heat fluxes.
The changes of the flow rates, composition
and
temperatures
of both phases during the condensation
are described by the appropriate
differential
mass
and energy balances.
Basic quantities
appearing
in these balances are
the mass fluxes of the condensing species and the flux
of energy transferred between the phases. Unequivocal definition of the fluxes requires knowledge of the
interfacial state variables, which determine the kinetics of the condensation.
To evaluate these variables
the relations
employed
are those which hold at
steady state for any cross-section
perpendicular
to
the interface:
-equality

of the mass fluxes at the interface

Nio = N,L
- energy balance
i
j-

i=l,2,...,n-1
at the interface

Nj AHj + a,(7, - Z-,) = k(T, - 7,-)

I

(1)

(2)

192
If the flow rates, composition
and temperatures
of
both phases are known in a given cross-section,
then
the matrices of the mass transfer coefficients, &
and &,
may be determined
using the procedure
described in refs. 11 and 12.
By introducing
the relations defining the mass
fluxes, eqns. (6)-(g), into eqn. (1) we obtain

CONDENSAT

n--l

jc,&(S

n--l

- xi) + -TIN= jc, B~(rj

y,d + Y,~N

i=l,2,...
which can be written

in a concise matrix

*n--l
form:

fMx, - x) + x,N = B%Y - ~1) + YIN

G,+dG,

GC

T, + dT,

G,+dG.

T,+fl,
5, + dX,

Ta+flo
v, + dv,

Fig. 1. Schematic diagram of concentration and temperature

profiles in a cross-sectional area of the condenser.

1
-z~+~+$
k

-equilibrium

relations

at the interface
i=l,2,...,n

-5, . . . 2-%I,,T*, PI

y,=.L(x,,,

(3)
(4)

i=

If we assume that the pressure P, the vapour

temperature
TG, the complete composition
of both
phases, yi and xi, and the coolant temperature
Tc
are all given for a certain cross-section
of the condenser, then 2n + 2 unknown variables may be calculated using eqns. (l)-(S),
namely n mole fractions
n mole fractions
ya (i =
y2(i=l,2,...,n),
temperature
TI and the
. . , n), the interfacial
t&~l.flux of the condensing
vapour N.
The mass flux of the ith component in the vapour
phase is given by
Nit

4.a

Y,

f
j=l

Nj

AGI

i = 1,2,.

. . ,n

(11)

where, as was pointed out, the equilibrium

constants
will, in general, depend on the composition
of the
liquid phase, the interfacial
temperature
and the
pressure.
For an ideal mixture, the equilibrium
constants
will be functions
of the temperature
and pressure
only:
K,

Pn(Td

(2)

Upon introducing
equilibrium
relation
matrix form

the diagonal
matrix
( 11) may be expressed

K, the
in the

(13)

that is,
YI = Kx,
Inserting
get

(14)
eqn. (14) into ( 10) and solving for x1 we

Y,N

i-1,2,...

,n-1

(6)

where the diffusional flux is

n-1
LX = c B?gAYj- Yj,)
(7)
j=l
For the liquid phase a similar relation is valid:
n-1
i=l,2,...,n-1
N,L = c &X&1 - Xi) + XiIN
j=

(10)

where E and p; are the (n - 1) x (n - 1) matrices of

mass transfer coefficients, and y, x, y, and x1 are the
(n - 1) x 1 column matrices of mole fractions in the
bulk vapour and liquid phases and at the interface,
respectively.
According to the assumptions
of the model the
mole fractions x,, and y, are related by the equilibrium formulae (3), which may be written as follows:
yi1 = Ki (x,, T,, P)

where

(9)

(8)

x [Y + mi)-VW

(1%

Each of the matrices of mass transfer coefficients

is a function of the total mass flux of the condensing
vapour N through the matrix of correction factors 8
[ 131, that is,
Bt; = B&G

(16)

BIL= &@L
where the matrices

(17)
&

and 8,

are functions

of the

193
following matrices:
&=NBo-

(18)

&=

(19)

NBC

The form of these functions depends on the mass

transport model employed.
Assuming that the positive directions of the fluxes
pertain to species leaving the vapour phase, the
following functions defining the correction matrices
are obtained [ 131:
-according

to the film theory

@G = @o[K - exp(

-W-

0, = h_[exp~~d - El - I
-according to the penetration theory
O,=exp(-

z)k-erf($)]-

(20)
(21)

(22)

interfacial temperature for the vapour composition

considered, namely T,(y). This mode of condensation is termed the local total condensation.
The second limiting case is obtained for very small
fluxes of the condensing vapour: N 40, that is,
@+O.
Making use of eqns. (25) and (27) we get for this
case the limiting value of the liquid-phase composition at the interface:
~~~ox,=(Bo-~~+K)-(~+PG-l~~~)

(30)
*L+O
Equation (30) was obtained by assuming a value
of zero for the total flux N, without discussing
further the mechanism of such a process. Owing to
the fact that in the condensation process the mass
transport is unidirectional, the value N = KY_r NJ
may be equal to zero only when all fluxes of the
condensing
species also approach zero (Ni +O,
i=l,2

O,=exp(-

$Z)[E+erf(-$5)]-

(23)

It has also been shown in ref. 13 that the limiting

values of the correction matrices are independent of
the mass transfer model used. Thus, for the gas
phase we have
Oor$o~co

for

&i+cc

(24)

Oo=E

for

&=O

(25)

while for the liquid phase

@L=o

for

cbI_+co

(26)

&=E

for

(PI_=0

(27)

Upon introducing eqns. ( 16)-( 19) into eqn. ( 15),

which defines the mole fractions at the interface, we
may transform it into the following form:
x1 = [@,--&&,-OL

+ K + O,-e&E

x (Y + %-4k+L-@LX)

- K)] --I
(28)

It follows from the above equation that the liquid

composition at the interface indeed depends on the
intensity of condensation, characterized by the magnitude of the tlux of the condensing vapour, N,
which appears in the matrices 0 and 4. Let us
examine more closely the change of x, as a function
of 8 and 9.
Using eqns. (24) and (26) it may be proved that

d_@_Xl

= Y

Thus, we reach an interesting conclusion: for very

large fluxes of the condensing vapour the liquid
composition at the interface becomes equal to that in
the bulk vapour. Since, according to the assumptions
of the model, there exists thermodynamic
equilibrium at the interface, the interfacial temperature
TI must be equal to the boiling point of the liquid
whose composition is equal to the bulk vapour composition (y,). This is the lowest possible value of the

,...,

n).

Therefore, in order to determine correctly the

concentrations at the interface, the interfacial energy
balance should be taken into account, with the individual mass fluxes given by eqn. (6).
Hence, after some transformations we obtain
N=

k(T, - Tc) - a;( TG - T,) -

j-1

IsI AHj

II

A&
(31)

AH;,

= 2 Y7AHj
j=- I

(32)

It may be seen from eqn. (31) that if N is to be

zero the following relations must hold:
Tc = TI = TG

&ir=O*Y,=Y,

(33)

i=l,2,...,n

(34)

Thus, no concentration gradients appear in the

vapour, and its interfacial composition is equal to
that of the bulk phase. Since thermodynamic equilibrium prevails at the interface, Y, ( =yJ is in equilibrium with x,, and, consequently, TI must be equal
to the dew point temperature of the vapour of
composition y, namely, T,(y). This mode of the
process is called the equilibrium condensation.
For finite values of N from the interval (0, co) the
interfacial temperature falls within the range
TB(

XI =

Y) < TI < T,(Y)

(35)

When TG > T,,(y), that is, when the vapour is

superheated, some temperature difference exists between the bulk vapour and the interface, but there is
no further driving force to take away the superheat
(Tc = T,,(y) = TI). Thus, cooling of the superheated
vapour may occur with simultaneous evaporation of
the condensate. Generally, however, in such instances (N + 0) the superheated vapour already undergoes cooling down to the dew point temperature
in the inlet part of the heat exchanger.

194
In the quantitative
description
of the condensation certain simplifying assumptions
are usually employed concerning
the mass transfer in the liquid
phase.
As has already been mentioned,
for large values
of N the correction
matrix e,_ tends to zero and,
consequently,
the matrix of transfer coefficients B:
also takes very small values. Moreover, the flow of
the condensate is usually laminar, which also leads to
very small mass transfer coefficients.
Hence, the following model of mass transport in
the liquid phase may be assumed:
and hence

Pi-0

I IL0

(36)

w-c-

TX)

NC

.m,

dT,
-=
dF

d Tc
-=+

(45)

G&&y

(46)
G&c
where the negative sign pertains to the vapour and
the coolant flowing cocurrently
with the condensate
(which, in turn, flows down the condenser under the
action of gravity).
In the detailed design calculations it is convenient
to introduce
a parameter
describing
the degree of
condensation,
dF

that is,

u = (Gco - GG)/GGO

N, z x,~N

which varies within the range [0, 11.

Inserting
o into eqns. (43))(46)
and using
assumptions
introduced earlier, finally we obtain
following differential equations:

(37)

With such an assumption

the calculations
become
considerably
simpler as the diffusional fluxes in the
liquid phase need no longer be determined. Equation
(28) may thus be reduced to
x, = [K + 8,-+,(E

-y

-K)]

N = [k(T, - TG) - az(T,

- K)]-*y

T,)]/AH,

X~I

(39)

i=l,2,...,n-1

l-v

dTo
---Z
dv

dTc
-=

(49)

W, - Tc) Go

dv

G&c

(50)

The cocurrent flow of the vapour, condensate and

cooling medium is assumed in these equations.
Moreover, in each cross-sectional
area of the condenser defined by the degree of condensation
v, the
following relations must hold which determine the
flow rates of both phases together with the average
composition
of the liquid:

(41)

Go=G&l-t))

(42)

xi=Ye-Ylv

where

(51)

G,_ = Go,,v

aE= 1 -

NCmx
exp( -NC,,,/c&

the
the

(38)

satisfying the limiting cases for Q. + co and &. + 0

derived using the general formula (28).
Finally, making use of the film theory we obtain
the following set of algebraic equations defining the
interfacial parameters and the total flux of the condensing vapour:
x, = [E - exp( -&)(E

dYi _- Yi

du-

(47)

(52)

-4
V

The heat
equation

3. Concentratioo
and temperature profdes
along the condense!r

F= Goo

transfer

dv/N

i=l,2,...,n-1
area

is calculated

(53)
using

the

(54)

The interfacial
state variables, determined
using
the relations
derived in the previous Section, unequivocally
define all the mass and energy fluxes.
These fluxes may now be employed in the appropriate mass and heat balances characterizing
the condenser analysed.
For the parallel flow of the vapour, condensate
and cooling medium the mass and heat balances are
given by the following set of differential equations:

do--0

(43)

dTo/dv

It shozld be noted that the intensity of condensation has a substantial

effect on the state variables of
the condensing
mixture. Applying
the conclusions
given in the previous Section, for the local total
condensation
we have

dri

i=l,2,...,n-1

and

d.vi

dF=

+QVi-yy,N)

i=l,2,...,n-I

(44)

= 0

(56)
that is, for large fluxes of the condensing
vapour its
composition
and temperature
do not change as the
condensation
proceeds.

195

4. Numerical solution of tbe model equations

In order to determine
from eqn. (54) the heat
transfer area required for the condensation
of a given
multicomponent
mixture, it is necessary to integrate
eqns. (48)-(50)
over the whole range of degrees of
condensation
(V = O-l).
The boundary
conditions
associated
with these
equations are defined by the inlet composition
and
temperature
of the vapour mixture:
To = Too,

i=l,2,...,n-I

Yi =y,

for v = 0

(57)

Depending on the direction of flow of the cooling

medium we thus have either an initial value problem
(cocurrent
flow: Tc = T,, for v = 0) or a boundary
value problem
(countercurrent
flow: T, = T,, for
v = 1).
The equations
analysed were integrated
numerically using the modified Euler method. Employing
certain special features of the right-hand
sides of
eqns. (48)-(50),
their partial analytical
integration
was carried out within a single integration
step. The
recurrent formulae which explicitly define the values
of yi, T, and T, at the end of each step were thus
obtained.
The use of such an algorithm
substantially
reduces the calculation
time with respect to the
fourth-order
Runge-Kutta-Gill
method, without diminishing the overall accuracy.
Thus, the numerical integration was performed on
the basis of the following recurrent formulae defining
the values of the parameter
at the end of each
integration
step:
vk+,=vk+Av

(58)

Fk+,=Fk+-Au

GGO

(59)

N/C

1 -v,

Yi,k+l =Xil,k +(Yi,k-Xi*,k)

1 _v

&+I

Tcc,k+,

T,,k

+(Tak

T,,k+(TC,k--T,,k)

T1.k)

;$I>

(61)

where

TC.k+l

=P

-k,

Go

-GzCpc Nk

(40), employing the Newton-Raphson

procedure for
an assumed value of the total flux of condensation
N.
The value of N was subsequently
verified using the
energy balance (41). If the error was found to be
larger than an arbitrarily
selected value E, N was
modified according
to the method of interpolation
and the interfacial state variables were recalculated.
The matrix function exp( -I&) appearing in eqn.
(39) was evaluated using Sylvesters theorem:
n-1
exp( -+o) = C Zo(&) exp( -*o,)
(66)
r-1
where the matrix coefficients Z,(A,) are defined by the
following formulae:
n-1

(62)
GG,k+I=GG~(l-vk+l)

(63)

G ,_,,~+,=GGoQ+,

(W

YzU-Yi,k+l(l-vk+l)
xi, k + I =
vk+l

The values of the interfacial state variables (x,, T,)

required
at each integration
step were calculated
iteratively
from the algebraic
equations
(39) and

-SE)

Z,(4) = ,_,

(67)

jg, (2,- 4)
j#V

in which D-r = A represents the inverse of the multicomponent

diffusion coefficients matrix and ;lj are
the eigenvalues of this matrix.
The elements of the inverse matrix D- = A are
given by

A..=J!L+

Din

2 22

(68)

D,

]=I
iti

The necessary eigenvalues

Iii of D-i = A were
computed by employing
two separate methods: the
characteristic
polynomial
for a ternary mixture, and
the transformation
method of Burghardt and Warmuzit%ki [ 141 for mixtures containing
more than
three components.
The mass transfer coefficients goi appearing
in
&ii.
doi = NIBoi
(70)
were calculated
from the known correlations
for
binary systems in which the binary diffusion coefficients have been replaced
by the eigenvalues
of the multicomponent
diffusion matrix, Li. So the
Sherwood and Schmidt numbers were evaluated as
follows:

Av

>

(D-

j=

s&ii

=&$j8

SCoi=*

Pd 1lU

(71)

The physical properties of the pure species in both

phases were taken from the literature [ 15, 161, while
those for
of the formulae
in ref.
At each
parameters

integration
the vapour

step the physicochemical

and liquid were
(TG and TL) and composition of the phases. The vapour-liquid
equilibrium
data were taken from refs. 18 and 19.

196

5. Numerical results ad

conclusions

In order to test the numerical procedures and

algorithms proposed, the calculations were carried
out for two different systems, a ternary mixture and
a five-component system.
As a ternary mixture the system benzene-toluenexylene, condensing inside vertical tubes of diameter
d = 0.021 m, was selected.
The local vapour mass and heat transfer coefficients Boi and cto were calculated for turbulent
flow with the aid of the following correlations:
Nu, = 0.026 Re,O.* Pr,13

(72)

Sh,, = 0.026 Reo.s Scoi3

(73)

For laminar flow the equations which approximate the theoretical Graetz solution were used.
The heat transfer coefficient for the condensate
film was evaluated from the formula [ 151
Nu, = ( Nu,~ + Nu,~) 4

In Table 1 the values of the final degree of

condensation, v,, above which condensation could
no longer occur, are given for certain temperatures
of the cooling medium. In a cross-section of the
condenser characterized by this particular value, vk,
the temperature difference between the interface and
the coolant dropped to a few tenths of a degree
Kelvin and the flux N tended to zero.
In all the calculations shown in Table 1, that is,
for both very large and very small intensities of
condensation, the method proposed here was convergent and stable.
Figures 2-6 illustrate the concentration and temperature profiles in the condenser as functions of the
degree of condensation for two values of the temperature of the cooling medium, T,-, = 293 K and

(74)

where
Nu, = 0.797 Re,-1
Nu, = 8.66 x lo-

(75)
Re,0.382 Prr,o,5689

(76)

The inlet vapour and coolant flow rates and the

coefficient of heat transfer into the cooling medium
were kept constant in all calculations:
Go0 = 1.89 x lO-5 kmol s-
Gco = 0.248 kg s-

T [Kl

t(c = 1745 W m-* K-

Tm-293

However, the initial composition and temperature

of the condensing mixture, as well as the inlet temperature of the cooling medium, were varied appreciably (the initial conditions
for which the
computations were performed are summarized in
Table 1). By making substantial changes in the initial
composition and, especially, in the temperature of
the coolant, the stability and convergence of the
numerical method were tested over a wide range of
condensation intensities. As the choice of the initial
temperature of the coolant, Too, affects the magnitude of the total flux of the condensing vapour, N, it
is possible to verify the method over the whole
region between the local total condensation and the
equilibrium condensation.
TABLE

I. Initial conditions

Temperature of cooling
medium, T,, (K)

YIO

Y20

293

323

0.33
0.99
0.001
0.001

0.33
0.001
0.99
0.001

x
x
x
x

calculations

lb

39l

fi - Tr

375.
I

92

a4

06

96

l.0

Fig. 3. Profiles of the dew point, boiling point and interface

temperatures as functions of the degree of condensation for the
mixture benzene-toluette-xyleneene(y,, = yrn = 0.330).

for the mixture benzene-toluene-xylene

Initial vapour
composition

x , numerical

Fig. 2. Bulk and interface. concentration profiles in the vapour

and liquid phases as functions of the degree of condensation for
the mixture benzenetohtene-xylene
(y,, = yss = 0.330).

343

348

352

353
x

315

382

", = 0.75

383

385

387

389

I& = 0.4

"k = 0.3

"k =o.z

"* =0.09

410

0, = 0.98
0, = 0.98
ut = O.%

performed; I+, maximal degree of condensation.

Q37-

a33
Q36_

Q35-

Q32-

a3(I

1
1

a2

a4

0.6

a8

1.0 v

Fig. 5. Liquid-phase
concentration
profiles as functions of the
degree of condensation
for the mixture benzen~toluene-xylene
(Y10 = y20 = 0.330).

a2

a4

aa

a6

1.0

Fig. 4. Vapour-phase
and interface concentration
profiles as functions of the degree of condensation
for the mixture benzenetoluene-xylene
(y10 = y,, = 0.330).

____
Tkl,

l-b

389

t
387 To-353

385 38338f 379-

ii;
0

0.1

d.2 -

a3

a4

a5

a6

a7

Fig. 6. Profrles of the dew point, boiling point and interface temperatures
benzene-toluene-xylene
( y10 = yzO= 0.330).

as

1
1.0

as functions of the degree of condensation

for the mixture

198
353 K, and thus for widely different condensation
intensities.
For To, = 293 K the process fully corresponds to
the local total condensation. This is demonstrated by
the fact that the vapour and liquid composition
remain unchanged along the condenser and that the
liquid composition at the interface is equal to that of
the bulk vapour (Fig. 2). The interfacial temperature, also constant throughout the condenser, is
equal to the boiling point of the liquid whose composition is yi (Fig. 3).
In Figs. 46, showing the course of condensation
at T,-, = 353 K, the differences between the interfacial liquid composition and that of the bulk vapour
are clearly visible; also, the interfacial temperature
differs from the boiling point of the liquid of the
same composition as the vapour phase. Even in that
case, however, the course of the process, characteristic of the final stages of condensation (v -+ l), becomes evident.
For v = 0.8, the liquid composition at the interface and that of the bulk vapour become equal; the
interfacial temperature T, also becomes equal to the
boiling point of the liquid phase, Ts. This is clear
evidence of the fact that, for such degrees of condensation, local total condensation occurs in the system:
the matrix & tends to infinity as the matrix of mass
transfer coefficients BG becomes equal to zero, which,
in turn, results from the vapour flow rate approaching zero. The analysis of this phenomenon is much
the same as that for binary mixtures [5].
Another example is a design procedure for a
condenser-evaporator
in which a five-component
mixture condenses in the intertubular space, while
the cooling medium, R-l 14, evaporates inside the
copper
tubes of d,Jdi= 20/16 mm and pitch
t = 1.5 do. The inlet vapour flow rate, temperature
and pressure are GGO= 40 kg SC, TGo = 448.2 K and
P = 0.1013 MPa, respectively. The evaporation of
R-l 14 occurs at constant pressure; it is also assumed
that the coefficient of heat transfer into the coolant is
constant and equal to 7500 W rn- K-.
Because of the nature of the process, the highest
evaporation temperature of R-l 14 at which the total
condensation of the mixture was still possible had to
be determined. The composition of the mixture is
given in Table 2.
The calculations were performed for various boiling points of R-l 14. At the boiling points equal to
293 K and 298 K and for the corresponding pressures P, = 0.187 and 0.221 MPa, the mixture condensed completely. For the boiling point of 303 K
TABLE

2. Composition

of the five-component

the condensation is no longer complete, since for

L)~= 0.99 the interfacial temperature T, reaches
303.3 K and the condensation ceases.
The concentration and temperature profiles calculated for Tco = 293, 298 and 303 K are shown in
Figs. 7-9.
Appreciable variation of the liquid and vapour
composition along the condenser, together with large
differences between the interfacial liquid composition
and that of the bulk vapour, which may be seen in
Figs. 7 and 8, suggest that the process analysed
differs from the local total condensation.
It is also evident from Fig. 9, which shows the
interfacial temperature profiles T,, that the process
does not approach that of the equilibrium condensation, as T, is markedly different from the saturation

Fig. 7. Vapour-phase and interface concentration profiles as functions of the degree of condensation for the five-component mixture (Table 2).

mixture

Component

Initial composition

2-Methylbutane
Ethylbenzene
Methylcyclohexane
Butylcyclopentane
n-Hexylcyclopentane

0.15
0.25
0.20
0.25
0.15

y,

Boiling temperature (K)

Molecular

301.0
409.3
374.1
429.9
476.3

72.15
106.17
98.19
126.24
154.30

mass

199
and becomes

identical

Tco=293 K

Yi

Xi=l+(Ki-l)exp(-~oi)

with that for binary

mixtures:
(77)

where
+oi = NIBoi

Fig. 8. Liquid-phase concentration

profiles as functions of the
degree of condensation for the five-component mixture (Table 2).

temperature
of the mixture, T,,. Even in this case,
however, the local total condensation
may be observed during the final stages of the process (v + 1),
thus confirming
theoretical
conclusions
reached in
the previous Sections. The numerical
example presented here is rather special from two points of view.
Firstly, the difference between the boiling points of
the individual
components
is large (about
175 K);
secondly, at the final stage of condensation
the difference between the interfacial temperature
and that of
the coolant does not exceed more than a few degrees
(for TcO = 303 K it falls to zero). Consequently,
the
condensation
intensities in the process studied cover
a relatively wide range of values.
As the number of components
increases, the calculations
become progressively
more laborious and
time-consuming.
This results mainly from having to
evaluate the matrix function exp( -4o) at each integration step, and thus determining
n - 1 eigenvalues
of the matrix of diffusion coefficients (n = number of
components).
As this is the most time-consuming
operation in the whole algorithm, a simplified calculational procedure has been proposed: assuming that
for the majority
of multicomponent
mixtures encountered
in practice the matrices of diffusion coefficients
are
diagonally
dominant
[ 141, the
non-diagonal
elements (and, consequently,
the diffusional cross-effects) may be neglected.
The matrix relation (39) is thus markedly simpler

(78)

leading to a fivefold reduction

of the calculation
time.
In order to compare the simplified method with
the exact results, the error involved in evaluating the
total flux of the condensing
vapour was determined
as a function
of the degree of condensation;
the
results are presented in Fig. 10. It may be seen from
this Figure that the error becomes appreciable
only
during the terminal stage of the process, when the
flux of the condensing vapour decreases as a result of
diminishing
temperature
differences.
Figure 11 illustrates the error resulting from the
use of the simplified
method in determining
the
length of the tubes of the condenser.
This error is
large only for the cases where the temperature
of the
cooling medium approaches
that of the interface.
Taking into account the fact that the example of
the design calculations
for the condenser-evaporator
presented in this work is rather special and that the
temperature
differences in industrial
condensers
seldom reach such low values, the simplified method
seems to be fully applicable to determining
the area
of heat transfer during multicomponent
condensation.

Nomenclature
C

molar density of fluid mixture, kmol me3

CP specific heat, kJ mol- K-
binary diffusion coefficient, m2 s-i
D,
D
multicomponent
diffusion coefficients matrix,
m* s-
d
tube diameter, m
E
unit matrix
heat transfer area, m*
F
molar flow rate, kmol s-
G
acceleration
due to gravity, m s-*
g
AH
molar enthalpy of evaporation,
kJ kmoll
diffusional flux of component
i, kmol m-* s-i
4
= Y,~/x,, equilibrium
constant
K
k
overall heat transfer coefficient, W m-* K-i
M
molar mass, kg kmoll
molar flux of component
i, kmol m-* s-i
Ni
N
=X7=, Nj, total molar flux of mixture,
kmol rnd2 ss
P
pressure, Pa
i, Pa
P&l3 vapour pressure of component
T
temperature,
K
V
degree of condensation
W
velocity of fluid, m s-l
mole fraction in liquid phase
xi
mole fraction in vapour phase
Yi

200
428-

a2

Q3

a7

a5

Q4

a9

T [Kl r

1s

333 1
3030

,I
02

a4

06

08

'0

Fig. 9. Profiles of the dew point, boiling point and interface temperatures as functions of the degree of condensation
mixture (Table 2).

for the five-component

201

18 -

~$298

293

29s

.Fo IK]
30:

4 _

I
46 -

-2 -

14

-3 -

12

-4 1

-5 -

Ta-293 K

I
I

b=D_L

,M)%

-6 _

-9

il

Fig. II. Error in the length of the condenser

tubes calculated
using the simplified method as a function of the cooling medium
temperature
for the five-component
mixture (Table 2).

Fig. 10. Error in the total condensation

flux calculated using the
simplified method as a function of the degree of condensation
for
the five-component
mixture (Table 2).

CL

Nu

transfer coefficient, W m- K-
transfer coefficients matrix,
kmol m-* s-
mass transfer coefficient, kmol m- 2 s-
= G,M,/dx,
wetting rate, kg m- s-
thickness, m
dynamic viscosity, kg m- s
correction factor matrix
thermal conductivity, W m- K-
eigenvalue of matrix D-, me2 s
density, kg m--3

heat
mass

= ad/l,

Nusselt number
/3/,IL, Nusselt number for
condensate
= CJ /A., Prandtl number
= wdplq, Reynolds number
=r&_,
Reynolds number for condensate
= v/( I/&), calculational Schmidt number for
component i
= /&d/C( I/&), calculational Sherwood
number for component i

Nur_ = a,(q,*/p,g)
Pr
Re
ReL
SCGi

Sk

Subscripts
:
D

refers to boiling point

refers to coolant
refers to dew point

refers to vapour
refers to interface
denotes component
refers to condensate film
refers to mixture
refers to wall
refers to inlet conditions

G
I
i
L
M
W
0

Superscript
denotes corrected
coefficients

heat and mass transfer

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