The Chenucal Engmeenng Journal 60 ( 1995) 105-l 10

Flow reactor models for fluid-fluid systems, based on the two-film theory
Jinfu Wang
Department ofChemtcal Engmeenng, Tsmghua Umverslty, BelJmg, Chtna
Received30 September1994,accepted21 March 1995

Abstract

Flow reactor models for hqmd-hqmd and gas-liquid systems are proposed m tius paper, based on the two-film theory m the isothermal
case The mathematical problem of a two-film mass transfer mechamsm accompamed by a chenucal lrreverslble first-order reaction IS treated
m a new way, with the aim of usmg the results to develop reactor design models Analytical solutions have been obtamed for the design
equation system which mvolves lmeardlfferentlal equations and an iteration procedure has been proposed to mtegrate the non-lmearchfferentlal
equation system The concentration profile, degree of mass extraction, reactant conversion and reactor capacity can be calculated easily by
means of the analytical solutions or a numerical procedure

Keywords Flow reactormodels, Fluld-fled systems, Two-film theory

1. Introduction
Many reactor types, such as tubular and various column
reactors, can be described by a flow model For two-phase
flow systems, smce materials m a separate phase must be
transferred m the other before reaction can occur, the design
equations ~111 contam both the mass transfer and chemical
rates Mathematical analyses of these problems are comph-
cated, so numerical techniques have usually been used m
solving the design problems m the past However, it IS dlffi-
cult to avold consldermg the convergence and stab&y of the
numerical methods [ 1,2] Therefore, It 1s important to
develop reactor design models with analytical solutions for
two-fluid systems
Various concepts of mass transfer at the interface were
proposed m the past These are the two-film concept [ 3,4],
the penetration concept [ 5,6], the film-penetration concept
[ 71 and the unsteady two-film concept [ 81 These concepts
were adopted respectively by Hatta [ 91, Danckwerts [ 10 1,
Huang and Kuo [ 1 l] and Wang and Langemann [ 121 m
developing the models for mass transfer accompamed by a
chemical reaction All the models developed m the past con-
cern only the mass transfer rate at the Interface and cannot
ascertam the concentration profiles m the main body of the
fluids and the conversion Obviously, they have some hml-
tatlons for the application of deslgnmg chemical fluid-fluid
reactors
Recently, Wullner [ 131 and Wang [ 141 have developed
mixed flow models for mass transfer accompanied by a chem-
lcal reaction, based on the film concept, but complete flow
models for two-phase reactors have not been reported In this
paper, design models of two-phase flow reactors for liquid-
liquid and gas-hqmd systems will be developed, based on
the two-film theory, where the variation of the gas hold-up
as well as the total pressure and volumetnc flow rate of the
gas phase along the flow direction can be taken mto account
In addition, we consider that an irreversible first-order reac-
tion occurs only m the liquid phase for the gas-liquid system
and m the second liquid phase for the hqmd-hqmd system
Furthermore, an isothermal case will also be considered
The design equations for a two-phase system consist of
two linear differential equations, if we consider a first-order
reaction and that the gas hold-up, total pressure and volu-
metric flow are constant otherwise, the design equations will
be non-linear In the case of linear design equations, an ana-
lytical solution IS achievable by means of the Laplace trans-
form However, it 1s lmposslble to solve the non-linear
differential equation system analytically To this end, an lter-
atlon procedure 1s proposed m this paper Usmg the given
analytical solutions or a numerical procedure, we can easily
calculate the concentration profiles m the bulks, degree of
mass extraction, reactant conversion and reactor capacity
2. Description of the two-film mechanism
For convemence, let us at first discuss the gas-hquld sys-
tem m which the gas phase behaves as an ideal gas Let A be

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106 J Wang/The Chemical Engmeenng Journal 40 (199s) 105-110

the reactant m the gas phase, which must enter and move into 3. Liquid-liquid systems
the liquid phase before it can react The two-film mechamsm
can be described by a set of equations, 1 e A flow reactor model for liquid-hqmd systems ts consld-
ered as m Fig 1 For slmphclty, we consider the case where
DAG d2pA
-- =o -6,<x<O (1) steady state plug flow takes place m the reactor Furthermore,
RT dx2 we assume that the volumetric flow rates along the flow dlrcc-
2 tlon remam constant The mole balance for a bulk consists of
DA, -
d2 =k,C, O<x<&_ (2) terms of flow, mass transfer across the film edge and chemical
reaction Thus, the mole balances concernmg the component
With the followmg boundary condltlons PA =PA,, at x = A for both the bulks may be wntten accordmg to Eqs (5)
-SG,CA=CAbatx=&,pA=HCAatx=O,and and (6) as

dPA RTDAL dCA dC.i,b

-=--
rLQl - = VE,U,cp[COSh(Ha) CA,, - KC,&2b] (9)
d.x DAG h dy
atx=O
Solving the above boundary value problem gives the con- dCA2b
LQ2 - = vElu,dcAlb - &A,,> - kV2bCA2b (10)
centration profile of the reactant A m the films, 1 e dy

cosh( Ha)PAb - HCA, where V,, = Ve2 - Vqu,6,, and r = 1 for countercurrent flow
k,RTHa and r = - 1 for cocurrent flow
PA=PAb- RTk,_Ha cosh(Ha) +Hk, smh(Ha)
The boundary condltlons will bc set up at the zero position
x 1+; of the reactor shown m Fig 1, so that the Laplace transform
( G 1 can be used simply m solving tbls boundary value problem
The boundary condltlons are

C,=cosh[Ha(l- jj]CAb y=o

+ ksAb - [k,_RTHa smh( Ha) + k&Z cosh( Ha) ] CA,, CA,, = CA2n

kLRTHa cosh( Ha) + k&Z smh( Ha)

Xsmh[Ha(l- $1
(11)
(4)

where kG=DAG/& kL=DALI&_ and Ha= &_(kA/DA,)“2

Q G$‘AP QLCA~
According to Flck’s law and differentiating Eqs (3) and
(4)) we obtain the mass flux NA at the film edges as (QICAIP) (&~CAZY)
y=o
DA
-- dPA

I
N~i.x=-t.x=- RT & x=_6G = rp[ cosh(Ha)P,, - Hc,,]
X
-
(5)
Y
dCA
N~ix=.s,= -DA x x=6L = dPAb - +cAb) (6) Y
c *
Y t dy
m which the abbreviations are defined as

[k,RT+k&] -I Ha=0
(7)
‘= { [k,RTcosh(Ha) +kJI smh(Ha)/Ha]-’ Ha>0 pAb
\
(CAlb)
+= :RT Hasmh(Ha)+Hcosh(Ha) (8) HCAb
\

(KcAZb)
If our system consists of two liquids rather than a gas and
y=L
hqmd, then we simply let the gas phase be the first liquid t
phase and make a senes of appropriate changes m termmol- QG~‘A~ QLCAP
ogy, such as changmgP,IRT to CA,, H to K, CA to CA2, etc
(QICAI~) I (Q&AzP)
The results for the two-liquid system retain the same form,
except that the constants R and Tdlsappearm the expressions Fig 1 Schemattc diagram of a two-flmd reactor model with r= 1
 J Wang /The Chemical Engmeenng Journal 60 (1995) 105-110 107

The above boundary value problem can be analytically mole balances for both bulks may be wntten according to
solved by means of the Laplace transform Accordmg to the Eqs (5) and (6) as
residue theorem, two first-order poles have been found for
rL d(PAbQo)
the transformed equations m this case The results of the -V~,cp[COSh(Ha)PAb-HCAb] =o (18)
FT dy
above boundary value problem give the concentration pro-
files m the bulks of the reactors as
de,,
LQL - - v’%%dPAb - &A,) + kAVLbCAb = o (19)
du
where v‘b= Vq- Ve,+z,S, and E,_+ 1 - k For this system
of differential equations, we will use similar boundary con-
ditions to those for the liquid-liquid system Thus, Eq ( 11)
x rQl (LQ2s + kAV2b
+ VW,Q~)CA,,- KVW,QQ~CA~~ becomes
rLQlQ2(s-s,)(s-s2)/(s--,)
y=o

Xexp(sy) (12) cAb = cA,

c A,=,$
!%, PAb = PA0 = (20)

This rnltlal value problem can slmllarly be solved analyt-

ically if we regard the total pressure m the reactor and the
x rVE,u,(pQ,CAlo+Q2[rLQls- VU,QcoW-WlC~, volumemc flow rate QG along the flow dlrectlon as being
rLQlQ2(s-sl)(s-s2)l(s-s,) constant The analytical solutions read
X exp(v) (13) 2
PAb = c &
where s, and s2 are the roots of the quadratic equation r=,

[rLQ,s- Vqa,cp cosh(Ha)] [LQ2s+kAVzb+ Vt-,a,cp+]

+ K( vE,U,Q)*= 0 (14)

The degree of mass extraction ( v~) and reactant conversion

x,, defined as
X exp(v> (21)

(15)
‘Ab=,$
s”J”3,

x = 1 _ QICAI,+QZCA,~
A (16)
QI~A,,+ QZ~AP,
x rVwl&@AO+ QL[~LQ& - Vw,rpRT cosh(Ha) 1CA,
can be calculated using Eqs ( 12) and ( 13) The reactor rLQ&_(~--~d (S-%)/(s-s,)
capacity SubJect to the mass transfer and the chemical reaction
can be obtained from this usmg the respective expressions
XexpW) (22)
where s1 and s2 are the roots of the quadratlc equation

[ rLQ,s - V.+x,cpRZ’
cosh( Ha) ]

E = <QI~AI~+ &~CAZ~)~A X [LQLs+ kA&_b

+ v6iw+] +RTH( VW&Q)‘= 0 (23)
x (17)
V
In some practical systems, the gas hold-up, the total pres-
sure and the volumetnc flow rate of the gas phase are vmable
along the flow dIrectIon In thus case, we must take mto
account the variation of the volumetnc flow rate and the
pressure drop For convemence, we consider a linear pressure
4. Gas-liquid systems
drop in the reactor as

A flow reactor model for gas-hqmd systems IS consldered

P=P,+AP; (24)
to be the same as for the hqmd-llqmd systems Slmllarly, the
108 J Wang/The Chemwal Engmeenng Joumal40 (1995) 105-110

The volumemc flow rate Qo should be E = QG~PAJIAI(L)

rl
RTV

r=l E = (QG,PA,+RTQLCA&AI(L)
x (31)
RTV
(25)
r=-1

and the gas hold-up is given by 5. Graphical representations

EGO contmuous gas phase

EG= (26) Using the analytical solutions of Eqs (21) and (25) as an
~~QolQo~ dlscontmuous gas phase
example of the apphcatlon of the flow reactor models for
Here, TJ,+~
and xAl are the local mass extraction degree and flmd-fluid systems, we have calculated the concentration pro-
reactant conversion, which are defined respectively as files of the bulks for a gas-hqmd system, usmg the model
parameters and constants given m Table 1, m the case with
QG~PAO constant P, QG and e. With the identical model parameters
r=l
and constants, but takmg mto account the pressure drop and
QGPA~
VA1 = (27) the vanatlon of the volumemc flow rate along the reactor, the
QGPA~
l- r=-1 concentration profiles also have been calculated numencally
QGGAO
by the Runge-Kutta method
The results are graphically presented m Fig 2 It can be
seen that the chemical reaction enlarges the mass transfer
QGCPAO +RTQLCAb
r=l velocity not only as a result of the film-enhancement effect
Q@Ab + RTQLCA,
but also as a result of the increase m the driving force for the
X AI = (28)
Q@Ab + RTQLCAb
l- r=-1 Table 1
QGGAO + RTQLCA,
Model parameters and constants

The overall mass extraction degree ,jA and reactant conver-

Vanable Unit Value Vanable Umt Value
sion xA are obtainable in the case of y = Z_.
The above dlfferentlal equations 1.e Eqs ( 18) and ( 19), V m3 5 a, m* mm3 285
are a non-linear dlfferentlal equation system, since the gas 60 0 35 0
hold-up lG and the volumetric flow rate Qo along the flow & m 5x10-5 ; m 1x lo+
DA, m2 s-l 1X1O-5 D, m* s-l 2x 10-g
duectlon are fUnCtlOnS OfpA, and CA, Furthermore, the mter-
facial area is also variable, because it equals V+a, There IS QW m3s-’ 5X1O-3 QL m3s-’ 1x 10-3
PM N m-* 1x103 CT*, kmol m-3 0
no analytical solution for this mltlal value problem However, R J kmol-’ K-l 8314 T K 298
it can be solved numerically using the followmg iteration P Nm-’ 1X10’ H J kmol-’ 1x lo6
procedure AP N mm2 5X104 r - 1

dPAb”
-= +’ V+“a,RTq
[COSh(Ha)pA,“+’
dy rLQG”

(29) v------v Ha = 0 25
6ooO
o----o Ha=10
dCAbn + ’ !%$% cpAbn+l _($cA~+l> 5ooo
-=

dr L
400
-- kAvLb” c ,,+I
(30)
LQL Ab 3oco

Now, we can find out the concentration profiles of the bulks, 2ooo
using any numerical integration method The calculation
needs only a few iterations when the concentration values loo0
from the analyucal solutions m the linear case are used as
mltlal values for the first iteration 0
0 2 4 6 8 10
The reactor capacity SubJeCt to the mass transfer and chem- Reactor coordmate y [m]
ical reactlon can be slmdarly obtained m this case, usmg the Fig 2 Comparison of the concentration profiles behveen the cases of P, Q.
respective expressions and co as constants (curves) and as vanables (symbols)
 J Wang/The Chemwal Engmeermg Journal 60 (1995) 105-110 109

mass transfer (the concentration difference between the

o-----o
Fig 3 Local extra&on degree as a function of Hatta number curves show
P, Q, and e. as constants, symbols show P, Q. and ho as vanables
Reactorcoordmate y [ml
Fig 4 Local conversion as a function of Hatta number curves show P, Q,
and co as constants, symbols show P, Qo and co as vanables
bulks), even though only the film-enhancement effect was
dlscussed m the hterature From a compmson of the concen-
tratlon profiles between the cases ofP, EGand Qo as constants
and as variables, the effect of the pressure and volumettlc
flow rate dlsttlbutlons along the reactor on the mass transfer
can be investigated Usually, increasing the system pressure
and interface area 1s advantageous to the mass transfer
Figs 3 and 4 show the local mass extraction degree qA1
and reactant conversion, xAlas a function of the Hatta number,
with the same model parameters and constants as used m Fig
2 Compansons between the cases of the system pressure,
volumetric flow rate and gas hold-up as constants (linear)
Ha = 10
and as variables (non-linear) are also represented graphically
in the figures The Overall mass extraction degree 7A and
reactant conversion XAcan be found at the position of y = L
The curve and symbols with Ha = 0 m Fig 3 represent the
mass extraction degree of physical gas absorption The devl-
atlons of the extraction degree m the lmear case from the non-
linear case decrease with acceleratmg reaction velocltles No
deviation m the extraction degree between both cases occurs
with fast reaction, such as Ha> 1 It 1s obvious that larger
deviations of the reactant conversion ought to appear m the
middle range of the Hatta number, smce the devlahon for the
reactant conversion does not exist m the case of physical
mass transfer
The relative volumetric flow rates of the gas phase (Qo/
Qco) are illustrated m Fig 5 These values are calculated
based on the same model parameters and constants as used
m the other figures The volumetnc flow rates along the reac-
tor depend on both the system pressure dlstrlbutlon and the
gas absorption velocity Increasing the system pressure and
the mass transfer velocity can lead to a decrease m the gas
volume As shown m Fig 5, the volumetnc flow rate
decreases monotonically for a slow mass transfer veloaty,
1 e a small Hatta number, while the mmlmum volumetric
flow rate occurs for a fast mass transfer velocity, i e a large
Hatta number This 1sbecause, for a high mass transfer veloc-
ity, the effect of the mass transfer on the decrease m gas
volume is greater than the effect of the system pressure

6. Conclusions

Design models of chemical flow reactors for fluid-fluid

systems can be developed based on the new model that
describes the two-film mass transfer mechamsm accompa-
_________ Ha = o 2
nied by a chemical reaction at the interface, as proposed m
----- Ha=04
this paper Analytical solution of the problem can be accom-
plished for the flmd-fluid system m the cases of constant gas
----- Ha = 0 8
hold-up, total pressure and volumetnc flow rate of the gas
phase, and for first-order reaction For gas-hqmd systems m
which the gas hold-up, total pressure and volumetric flow rate
061 s “““.“*‘I “I a ” ’ ” ” of the gas phase vary with the reactor length coordinate,
0 2 8
React: coordmate6y [m] or where a non-first-order reaction occurs, a differential
Fig 5 Volumetnc flow rate as a function of Hatta number equation system that mvolves two non-linear differential
110 J Wang /The Chemtcal Engmeenng Journal 60 (1995) 105-l IO

equations must be solved To this end, an Iteration procedure R gas constant (J kmol-’ K-l)
has been proposed T temperature (K)
Using the analytlcal solutions and/or the lteratlon proce- V reactor volume ( m3)
dure given m this paper, the concentration profiles m the X length coordinate m direction of dlffuslon (m)
bulks, mass extractlon degree and reactant conversion - X reactant conversion
which all are important for designing fluid-fluid reactors - Y length coordinate m dlrectlon of flow (m)
can easily be calculated, as long as the model parameters are
known Thus, the model with analytlcal solutions can be Greek letters
directly used to design plug flow reactors for two-fluid sys-
tems m the lmear case, and the iteration procedure can be s thickness of dlffuslon film (m)
used m the non-linear case Furthermore, they can also be CL hqmd hold-up
used to determine the optimum operating condltlons of a two- Y stolchlometrlc coefficient for formed gas, A + y gas
fluid phase reactor Another important apphcatlon of these K phase dlstrlbutlon coefficient
models 1s the estimation of the model parameters for an mass extraction degree
unknown system The model parameter estlmatlon 1s con- z, 4 abbreviations defined m Eqs (7) and (8)
venient using the present models, because only measurements
of the concentrations at the reactor exit need to be taken Subscrtpts
In addition to the above apphcatlons, the reactor model
with analytical solutions can be applied m the followmg two reactor zero position
aspects First, it can be used m testing complex reactor mod- first liquid phase
els For instance, one can use it to check a dlsperslon model second liquid phase
for the dispersion effect on the mass transfer and reactant reactant A
conversion It can also be used to investigate the effect of the bulk
non-linear factors on the mass transfer and reactant conver- gas phase
sion, as m this paper Secondly, the analytlcal solutions can local
conveniently provide mltlal values for numerlcal iteration liquid phase
procedures It will help also, even though the dispersion effect
1s taken mto account Thus, it not only can accelerate the input
convergence of the numerical procedures and save on a great output
amount of computer resources but also can improve the sta- mass transfer
bility of many numerical methods chemical reaction

Appendix A: nomenclature References

[ 1I T Y Na, Computatronal Methods m Engtneenng Boundary Value

a, mterfaclal area per volume of first or gas phase (m’ Problems, Acadenuc Press, New York, 1979
mW3) [21 ES Lee, Quasihneanzahon and Invariant Imbeddtng, Acadermc
C concentration (kmol mP3) Press, New York, 1968
D molecular dlffuslon coefficient ( m2 s- ’ ) [3] W G Whltman, Chem Metal1 Eng,29 (1923) 146-148
141 W K Lewis and W G Whltman, Ind Eng Chem , 16 (1924) 1215-
E reactor capacity (km01 m-3 s-‘)
1220
H Henry’s law constant (J kmol- ‘) [5] R Hlgble, Trans Am Inst Chem Eng ,35 (1935) 365
Ha Hatta number defined m condltlons for Eqs (3) and [6] P V Danckwerts, Imf Eng Chem ,43 (1951) 1460-1467
(4) [7] H L Toor and J M Marchello, AIChE J, 4 (1958) 97-101
reaction rate constant (s-l) [81 J Wang and H Langemann, Chem Eng Technol , 17 ( 1994) 280-
kA
284
k mass transfer coefficient (m SC’)
[9] S Hatta, Tech Rep Tohoku Imp Umv , 10 (1932) 119-135
L reactor length (m) [lo] P V Danckwerts, AIChE J, I ( 1955) 456-463
N mass flux (km01 me2 s-‘) [ll] CJ HuangandCH Kuo,AIChEJ,9(1963) 161-167
P partial pressure (N mP2) [ 121J Wang and H Langemann, Chem Eng Scz,49 ( 1994) 3457-3463
P total pressure of the system (N mP2) [ 131 G Wullner, Modelle Statlonarer Zweiphasen-DurchfluB-Reaktoren
mu und ohne Dlffuwonsgrenzsclucht, Dmsertatton, Umverslty of
AP pressure drop of the system (N mP2)
Paderbom, 1989
Q volumetric flow rate ( m3 s - ’ ) [141 J Wang, Erwelterung der Zwelfilmtheone des Stoffaustausches,
r flow status Dusertatron, Verlag Shaker, Aachen, 1994