Brazilian Journal

of Chemical ISSN 0104-6632

Printed in Brazil
Engineering
Vol. 20, No. 04, pp. 375 - 390, October - December 2003

EXPERIMENTAL ANALYSIS AND EVALUATION

OF THE MASS TRANSFER PROCESS IN A
TRICKLE-BED REACTOR
J.D.Silva2∗, F.R.A.Lima1 C.A.M.Abreu2 and A.Knoechelmann2
1
Nuclear Energy Department, Federal University of Pernambuco (UFPE), Phone (081) 3271-8251,
Fax (081) 3271-8250, Av. Prof. Luiz Freire 1000, 50740-540, Recife - PE, Brazil.
2
Chemical Engineering Department, Federal University of Pernambuco (UFPE), Phone (081) 3271-8236,
Fax (081) 3271-3992, R. Prof. Artur de Sá, 50740-521, Recife - PE Brazil.
E-mail: jornandesdias@yahoo.com.br

(Received: January 26, 2002 ; Accepted: May 29, 2003)

Abstract - A transient experimental analysis of a three-phase descendent-cocurrent trickle-bed H2O/CH4-

Ar/γ-Al2O3 system was made using the stimulus-response technique, with the gas phase as a reference.
Methane was used as a tracer and injected into the argon feed and the concentration vs time profiles were
obtained at the entrance and exit of the bed, which were maintained at 298K and 1.013 105 Pa. A
mathematical model for the tracer was developed to estimate the axial dispersion overall gas-liquid mass
transfer and liquid-solid mass transfer coefficients. Experimental and theoretical results were compared and
shown to be in good agreement. The model was validated by two additional experiments, and the values of the
coefficients obtained above were confirmed.
Keywords: trickle-bed, mass transfer, three-phase reactor, methane gas tracer, transient.

INTRODUCTION development of chemical processes such as catalytic

Analysis of the response of a system to an input
disturbance is a well-established technique for
studying the mixing characteristics of many types of
equipment. This type of procedure referred to as the
study of dynamic processes has been applied to, for
example, heat exchangers, distillation columns and
chemical reactors (Silva et al.,1999, 2000a,b; Lamine
et al., 1996; Tsamatsoulis and Papayannakos, 1995;
Ramachandran and Chaudhari, 1983; Iliuta et al.,
1997; Iliuta et al., 1999).
Trickle-bed reactors with cocurrent downflow of
the gaseous and liquid phases have been utilized in
several catalytic processes (Ramachandran and
Smith, 1979; Silva, 1996; Al-Dahhan et al., 1997;
Attou et al., 1999; Chin and King, 1999; Funk et al.,
1990; Gallezot et al., 1998; Iliuta et al., 1997; Jiang
et al., 1999). These reactors can be used in the
*To whom correspondence should be addressed
hydrodesulfurization, production of calcium acid
sulfite, oxidation of formic acid in water, synthesis
of butynediol, production of sorbitol, hydrogenation
of aniline to cyclohexylaniline and oxidation
of sulfur dioxide on activated carbon (Larachi et
al., 1991; Burghardt et al., 1990; Burghardt et al.,
1995; Gianetto and Specchia, 1992; Latifi et al.,
1997; Pawelec et al., 2001; Pironti et al., 1999;
Rajashekharam et al., 1998; Wu et al., 1996; Reinecke
et al., 1998).
Three-phase reactions in these reactors may be
limited by effects related to the availability of the
surface of the catalyst to the gas. In trickle-bed
reactors these restrictions may be attributed to gas
solubility, mixing in the liquid phase or gas-liquid
and liquid-solid mass transfer limitations.
Mathematical modeling of these three-phase
reactors may involve the mechanisms of forced
376 J.D.Silva, F.R.A.Lima C.A.M.Abreu and A.Knoechelmann

convection, axial dispersion, interphase mass ∂ Cr ( r, t ) De ∂  2 ∂ Cr ( r, t ) 

transport, intraparticle diffusion, adsorption and HS (1 + ρP K A ) = r  (3)
∂t r2 ∂ r  ∂r 
chemical reaction. Normally, these models are
constructed relating each phase to the others.
The initial and boundary conditions for the above
In pioneering work Ramachandran and Smith
equations are respectively
(1979), proposed a plug-flow model to describe the
adsorption and reaction of the gas on the catalytic Equation 1:
surface. In this work an axial dispersion model for
the liquid phase, which involves only the effects of CG ( z, ) ∀z = 0 ; CG ( 0, t ) = CG, 0 (4)
∀t
adsorption is reported. Emphasis was placed upon
evaluation, of parameters Dax, KGL and kLS, the Equation 2:
mixing and mass transfer coefficients of the gas
component. CL ( z,0 ) = 0;
∀z

∂ CL ( 0, t ) VSL
MATHEMATICAL MODEL = C L ( 0, t ) ; (5)
∂z Dax ∀t
∀t

The theoretical model described here is one- ∂ CL ( L, t )

dimensional and based upon the concentration of the = 0
gas tracer in the gas, liquid, and solid phases during ∂z ∀t
cocurrent operation (Silva et al., 2000a; Burghardt et
al., 1990; Ramachandran and Smith, 1979; Iliuta et al., Equation 3:
2002). The model adopted for the gas tracer within
these phases is constrained by the following ∂ C r ( 0, t )
Cr ( r,0 ) = 0; = 0;
simplifications: (i) the system is isothermal; (ii) the gas ∀r ∂r ∀t (6)
phase is modeled as a plug flow; (iii) the liquid phase is ∂ Cr ( R, t ) k
modeled taking axial dispersion into account; (iv) the = LS CL ( z, t ) − Cr ( R, t ) 
system operates with partial wetting of the bed; (v) ∂r ∀t
De  ∀t 

there is intraparticle diffusion in the pores of the

spherical catalytic particle; (vi) rapid adsorption The superficial velocities in Eqs. 1 and 2 may be
equilibrium is achieved in the system; (vii) the system determined from the following empirical models:
operates with a small concentration of the tracer in superficial velocity of the liquid phase (Hutton et al.,
order to minimize disturbances to reactor conditions. 1974):
Based on these simplifications, the mass balance
equations that describe the transient behavior of this H3d,L ρL g cos 2 β
system are given by the following coupled partial VSL =
( HS + Hd,L )
2 2
2µ L a GL
differential equations:
(7)
∂ CG ( z, t ) ∂ CG ( z, t )  H3 
 d, L cos 2 β 
H d,G + VSG = +
∂t ∂z  3µ L a GL ( HS + H d,L ) 
2 3
(1)  
−δGL  
− K GL a GL  HCG ( z, t ) − CL ( z, t )  2
 H d,L c os3 β (1 − HS − H d,L ) 
 3 
 2µ L a GL ( HS + H d,L ) 
2
∂ CL ( z, t ) ∂ CL ( z, t )  
H d, L + VSL
∂t ∂z
where δGL is given by
∂ 2 CL ( z, t )
= Dax  8.5µ a 2 G  µG a P  
2 0 .1
∂z 2 =
aP GG
 
G P G
δGL + 
(2)  ρG ρG  G G  
+ K GL a GL  HCG ( z, t ) − CL ( z, t )    (8)
1
(1 − HS − Hd,L )
3
−f e k LSa P CL ( z, t ) − Cr ( R, t ) 
 ∀t 

Brazilian Journal of Chemical Engineering

 Experimental Analysis and Evaluation of the Mass Transfer Process 377

superficial velocity of the gaseous phase (Specchia ∂ Γ r ( 0, t A )

and Baldi, 1977): Γ r ( η,0 ) = 0; = 0;
∀η ∂η ∀t A
1 − (1 − HS − H d,G ) 
2 (16)
= K1  ∂ Γ r (1, t A )
( )
δGL  µ V
G SG = Sh Γ L ( ξ, t A ) − Γ r (1, t A )
(1 − HS − Hd,G )
3
∂η ∀ tA
(9) ∀t A

1 − (1 − HS − H d,G ) 
+ K2   ρ V2 )
G SG The dimensionless parameters in Eqs. 11 to 16
(1 − HS − Hd,G )
3
are defined as

Equations 1 to 3 and their initial and boundary K GL a GL L H VSL H d,G

conditions can be analyzed with dimensionless α= ;κ =
VSG VSG H d,L
variable terms from the following ratios:
(17)
K GL a GL L H d,G f e a p k LS L H d,G
CG ( z, t ) C L ( z, t ) γ= ;ϑ =
Γ G ( ξ, t A ) = ; Γ L ( ξ, t A ) = ; VSG H d,L H d,L VSG
CG,0 CG,0 H

C r ( r, t ) VSG t (10) VSG L H d,L De H d,G L

Γ r ( η, t A ) = ; tA = ; PE∗ = ; λ= 2
CG,0 H H d,G L
Dax H d,G R HS (1 + ρP K A ) VSG
z r (18)
ξ = ; η= k R V L
L R Sh = LS ; PE = SL
De Dax
Thus, Eqs. 1 to 3 are rewritten as

∂ ΓG ( ξ, t A ) ∂ ΓG ( ξ, t A )
+ SOLUTION OF SYSTEM EQUATIONS
∂ tA ∂ξ
(11) The partial differential equation system defined
+αΓ G ( ξ, t A ) = αΓ L ( ξ, t A )
by Eqs. 11 to 13 may be solved in the Laplace
domain, as reported in previous studies (Silva et al.,
∂ Γ L ( ξ, t A ) ∂ Γ L ( ξ, t A ) 1 ∂ Γ L ( ξ, t A )
2
2000b; Iliuta et al.,1999; Burghardt et al., 1995;
+κ −
∂ tA ∂ξ PE∗ ∂ ξ2 Ramachandran and Smith, 1979).

( )
= γΓG ξ, t A − γΓ L ( ξ, t A ) (12)
dΓ∗G ( ξ,s )
s Γ∗G ( ξ,s ) + + α Γ∗G ( ξ,s ) = α Γ∗L ( ξ, s ) (19)
dξ
−ϑ Γ L ( ξ, t A ) − Γ r (1, t A ) ∀t 


∂ Γ r ( η, t A ) d Γ∗L ( ξ,s ) 1 d Γ L ( ξ, s )
2 ∗
∂  2 ∂ Γ ( η, t A ) 
λ s Γ∗L ( ξ,s ) + κ −
= 2 η  (13) dξ PE∗ dξ 2
∂ tA η ∂η  ∂η 

The dimensionless initial and boundary = γ Γ∗G ( ξ,s ) − γΓ∗L ( ξ,s ) (20)
conditions for Eqs. 11, 12 and 13 are given by
−ϑ Γ∗L ( ξ,s ) − Γ∗r (1,s ) 
 
Γ G ( ξ,0 ) =0; Γ G ( 0, t A ) =1 (14)
∀ξ ∀ tA
∂  2 ∂ Γ r ( η,s ) 
∗
λ
s Γ∗r ( η,s ) = 2 η  (21)
η ∂ η  ∂ η 
ΓL ( ξ,0) = 0; ∂ΓL ( 0,t A ) = PE ΓL ( 0,t A ) ;
∀ξ ∀tA
∂ξ ∀tA The boundary conditions in the Laplace domain are
(15)
defined by
∂ΓL (1,t A )
=0
∂ξ ∀tA Γ∗G ( 0,s ) = 1 s (22)

Brazilian Journal of Chemical Engineering, Vol. 20, No. 04, pp. 375 - 390, October - December 2003
378 J.D.Silva, F.R.A.Lima C.A.M.Abreu and A.Knoechelmann

d Γ∗L ( 0,s ) d Γ∗L (1,s ) and

= PE Γ∗L ( 0, s ) ; =0 (23)
dξ dξ
d3Γ∗L ( ξ,s ) d 2 Γ∗L ( ξ,s )
+ δ (s)
dξ 3 dξ 2
dΓ∗r (1,s ) (30)
= Sh Γ∗L ( ξ,s ) − Γ∗r (1,s )  ;
dη   dΓ∗L ( ξ,s )
(24) − K1 ( s ) + K 2 ( s ) Γ∗L ( ξ,s ) = 0
dξ
dΓ∗r ( 0, s )
= 0
dη where

To find the relationship between Γ∗L(ξ, s) in the K 2 ( s ) = αγ

 − a1 ( s ) ν ( s )  PE ;
∗

liquid phase and Γ∗r (1, s) at the outer surface of the

catalyst particle, Eq. 21 was solved with the K1 ( s ) = a1 ( s ) κ + ν ( s )  PE∗ ; (31)
boundary conditions in Eqs. 24 (Appendix A).
δ ( s ) = a1 ( s ) − PE∗ κ 
 
Sh Γ∗L ( ξ,s )
Γ∗r (1,s ) = ; The formal solutions for Eqs. 29 and 30 were
{φ  ( s )  + Sh − 1}
 ( s )  cot gh φ suggested by Ramachandran and Smith (1979) and
(25) were applied here in the following forms:
s2
 ( s )  = λ
φ
3
Γ∗G ( ξ,s ) = ∑ fi ( s ) exp λ
 i ( s )  ξ;
Eq. 25 was introduced in to Eq.20 and Eqs. 19 and i =1
20 were rearranged as (32)
3
fi ( s )
d Γ∗G ( ξ,s )
Γ∗L ( ξ,s ) = ∑ λ
 ( s ) − a ( s ) 
i
α  i ( s )  ξ
exp λ
+ a1 ( s ) Γ∗G ( ξ,s ) = α Γ∗L ( ξ,s ) (26) i =1
dξ
where
1 d 2 Γ∗L ( ξ, s ) −κ
d Γ∗L ( ξ, s )
1
PE∗ dξ 2 dξ λ1 ( s ) = J ( s ) + T ( s ) − δ ( s ) ;
(27) 3
+ν ( s ) Γ∗L ( ξ,s ) = −γ Γ∗G ( ξ,s ) 1
λ 2 ( s ) = −  J ( s ) + T ( s )  − ; (33)
2
where
1 3
− δ (s) + i  J ( s ) − T ( s ) 
 ( s )  cot gh φ
φ  ( s )  − 1 ; 3 2 
R (s) =
{  ( s )  cot gh φ
φ  ( s )  + Sh − 1 } 1
(28) λ 3 ( s ) = −  J ( s ) + T ( s ) 
2
ν ( s ) = s + γ + ϑR ( s )  ; a1 ( s ) = ( s + α ) (34)
1 3
− δ (s ) − i  J ( s ) − T ( s ) 
Combining Eqs. 26 and 27 gave two third-order 3 2 
linear ordinary differential equations with constant
coefficients for Γ∗G (ξ, s) and Γ∗L (ξ, s): and

d3Γ∗G ( ξ,s ) d 2 Γ∗G ( ξ,s )  9δ ( s ) K ( s ) + 27K ( s ) + 2 δ ( s )  3 

   ;
+ δ (s) H (s ) = − 
1 2

dξ 3 dξ 2 54
(29)   (35)
1
dΓ∗G ( ξ,s )  3 2 2
− K1 ( s ) + K 2 ( s ) Γ∗G ( ξ,s ) = 0 J ( s ) = H ( s ) + Q ( s )  +  H ( s ) 
dξ  

Brazilian Journal of Chemical Engineering

 Experimental Analysis and Evaluation of the Mass Transfer Process 379

 3K ( s ) + δ ( s )  2  the gaseous phase was given by

 1   ;
Q (s) = −  
 9  D1 ( s )
(36) Γ∗G ( ξ,s ) = exp λ1ξ
 3
1
2 2 D (s)
T ( s ) = H ( s ) −  Q ( s )  +  H ( s )   (37)
  D2 ( s ) D3 ( s )
+ exp λ 2 ξ + exp λ3ξ
D (s ) D (s)
The boundary conditions, Eqs. 22 and 23, were
used to obtain the integration constants of Eq 32 Determinants D1(s), D2(s) and D3(s) were
(Appendix C), so, the response for the gas tracer in introduced in to Eq. 37 (Appendix C), resulting in

Γ∗G ( 0,s )
Γ∗G ( ξ,s ) =
D (s)
{V ( λ
∗
1 2 ( s ) , λ3 ( s ) ,a1 ( s ) ) exp λ1 ( s ) ξ + V2∗ ( λ1 ( s ) , λ3 ( s ) ,a1 ( s ) ) exp λ 2 ( s ) ξ + V3∗
(38)
( λ1 ( s ) , λ 2 ( s ) ,a1 ( s ) ) exp λ3 ( s ) ξ  }
where V1∗, V2∗and V3∗ are functions defined in the Laplace domain and are given in Appendix C.
For ξ = 1 it was possible to obtain the response of the gas tracer at the exit of the fixed bed with Equation 39:

ξ=1
Γ∗G (1,s ) = ∫Γ ( ξ,s ) δ ( ξ − 1) dξ
∗
G (39)
ξ= 0

Thus

Γ∗G ( 0,s )
Γ∗G (1,s ) =
D (s) 
{  V1∗ ( λ 2 ( s ) , λ3 ( s ) ,a1 ( s ) ) exp λ1 ( s ) + V2∗ ( λ1 ( s ) , λ 3 ( s ) ,a1 ( s ) ) exp λ 2 ( s ) + V3∗
(40)
( λ1 ( s ) , λ 2 ( s ) ,a1 ( s ) ) exp λ3 ( s )}
The transfer function of the system was defined by the ratio of the exit function to the entrance function
[G∗(1, s) = Γ∗G (1, s)/ Γ∗G (0, s)], so the final transfer function was

G ∗G (1,s ) =
1  ∗
D (s)
{
V1 ( λ 2 ( s ) , λ3 ( s ) ,a1 ( s ) ) exp λ1 ( s ) + V2∗ ( λ1 ( s ) , λ 3 ( s ) ,a1 ( s ) ) exp λ 2 ( s ) + V3∗
(41)
( λ1 ( s ) , λ 2 ( s ) ,a1 ( s ) ) exp λ3 ( s ) }

The theoretical concentration at the exit of the where the Laplace variable (s) was substituted by iω
fixed bed, ΓG(1,tA)kCalc, was calculated by the in the Fourier domain.
convolution of the experimental concentrations ΓGExp
(iω) with GG∗(1, iω). ΓG(1,tA)kCalc was obtained by
numerical inversion, using the numerical fast Fourier MATERIALS AND EXPERIMENTAL
transform (FFT) algorithm (Cooley and Twkey, METHODOLOGY
1965) that changed the time domain according to
following equation: To study the axial dispersion and the mass
transfer effects, a three-phase gas-liquid-solid reactor
was mounted according to Fig 1. The assembled
= TF−1 Γ EExp ( i ω) ∗ G∗G (1,i ω) 
Calc
 G (1, t A )  k
Γ
 
(42) system consisted of a fixed bed with a height of 0.16

Brazilian Journal of Chemical Engineering, Vol. 20, No. 04, pp. 375 - 390, October - December 2003
380 J.D.Silva, F.R.A.Lima C.A.M.Abreu and A.Knoechelmann
m and an inner diameter of 0.03 m; catalytic particles
were contacted by a cocurrent gas-liquid downward
flow. Experiments were conducted under conditions
such that the superficial velocities of the gas and
liquid phases were maintained within the trickle-bed
regime (Ramachandran and Chaudhari, 1983) VSL in
the range of 10-4 m s-1 to 3 10-3 m s-1 and VSG in the
range of 2 10-2 m s-1 to 45 10-2 m s-1.
The gas phase (4% volume Ar +CH4), flowing
downward cocurrently in contact with 70.00g of the
solid bed (γ-Al2O3, CGO-70, Rhone-Poulenc), was
continuously measured using a thermal conductivity
detector (TCD) coupled to an AD/DA interface. The
tracer was turned on and off at differing superficial
velocities; deviations in the signal from its baseline,
negative steps, provided a measurement of its
concentration versus time at the entrance and exit of
the bed.
The methodologies applied to evaluate the axial
dispersion and the mass transfer parameters for the
CH4 – Ar – H2O / γ-Al2O3 system were the
following:
- analysis of the negative - step curves at the entrance
and exit of the bed;
Figure 1: Experimental Setup
Brazilian Journal of Chemical Engineering
- residence time distribution (RTD); determination
by the method of moments applied to the normalized
curves. A comparison of experimental results with
the expressions obtained from the transfer function
(GG∗(1,s); Eq.41) as developed for this system;
- evaluation of the model parameters (Dax, KGL, kLS)
used as initialization values when obtained by the
method of moments;
- optimization of the model parameters by comparing
the calculated values of concentration with the
experimental data.
To calculate the concentrations within this
numerical model, several numerical values for the
CH4–Ar–H2O / γ-Al2O3 system are required; in Table
1 these values, obtained under similar experimental
conditions, are listed (Silva, 1996).
Performance of the trickle-bed is affected by
many factors, such as interphase mass transfer,
intraparticle diffusion, axial dispersion, gas and
liquid holdup and partial wetting. These factors are
incorporated into this model. As the liquid flow was
maintained constant, Silva’s tabulated values
representing liquid holdup (Hd,L) and partial wetting
(fe) (1996) were adopted.
B - 101: Vacuum pump;
C - 101: PC-585; F: Filter;
C - 102: Gas chromatography (CG-370);
G - 101: Nitrogen (N2);
G - 102: Hydrogen (H2);
G - 103: Argon (Ar); M: Pressure gauge;
P - 101: Acquisition data plate (AD/DA);
R - 101: Three-phase fixed-bed reactor;
T - 101: Distilled water tank;
VS: Solenoid valve;
V: Passage valves.
 Experimental Analysis and Evaluation of the Mass Transfer Process 381

Table 1: Properties, parameters and operational variables for the H2O/Ar-CH4/γ-Al2O3

system (Silva, 1996).

Numerical Values
-4
µL, kg m s -1 -1
8.91 10 VSG, m s-1 29.46 10-3 R, m 1.60 10-3
µG, kg m-1 s-1 1.23 10-5 VSL, m s-1 1.91 10-4 σL, kg s-2 7.22 10-2
ρL, kg m-3 1.01 103 aGL, m2 m-3 8.13 104 fe 3.50 10-1
-1 2 -3 3
ρG, kg m -3
6.63 10 aP, m m 1.14 10 H 5.70 10-2
δGL, kg m-2 s-2 1.14 101 KA, m3 kg-1 6.45 10-4 De, m2 s-1 4.56 10-3
ρP, kg m-3 3.15 103 L, m 1.60 10-1 εex 3.90 10-1
Hd,G 2.00 10-1 DP, m 3.20 10-3 W, kg 7.00 10-2
-1 -2 -1 -4 -2
Hd,L 5.40 10 GL, kg m s 5.07 10 g, m s 98.10 10-1
HS 2.60 10-1 GG, kg m-2 s-1 1.74 10-5 DR, m 3.210 10-2

RESULTS AND DISCUSSION coefficients for differing gas - phase flow are
reported below in Table 2.
Experiments were conducted at a constant liquid In Figs. 2 and 3 results of the two sets of
flow of QL = 0.50 10-6 m3 s-1 and the gas phase was experiments presented show normalized profiles for
varied in the range of QG = (41.69 to 9.97) 10-6 m3 s- concentration of gas tracer as a function of time.
1
. The mean residence times, (tM)G = (tM)S,G – (tM)E,G, A model validation process was established by
were obtained from the experimental curves; (tM)G comparing the theoretical results obtained with the
was found to be in the range of 0.43 s to 8.47 s. values of the optimized parameters and the
The axial dispersion coefficient and the gas-liquid experimental data for two test cases. These results,
and liquid-solid mass transfer coefficients were presented in Figures 4 and 5, confirm that this
determined simultaneously by comparison between reactor is represented by this model.
the experimental and theoretical data, obtained at the The axial dispersion and the interphase mass
exit of the fixed bed, subject to the minimization of transfer phenomena characterized in the three-phase
objective function (F) where process studied are influenced by changes in gas
flow. It was noted that at fixed liquid flow rates and
2 with fixed liquid retention and partial wetting of the
∑ {[Γ }
N
F= G (1, t A ) ]Exp
k
− [ Γ G (1, t A ) ] Calc
k (43) bed, the highest gas-liquid and liquid-solid mass
k =1 transfer effects were obtained for the highest gas -
phase flow. Consequently, parameters Dax, KGL and
The initial values of Dax, KGL and kLS were kLS can be described by empirical correlations.
Correlations taken from Stiegel and Shah (1977),
determined from the first absolute moment, (µ1)G, of
Fukushima and Kusaka (1977) and Chou et al.
the transfer function. The first absolute moment can
(1979) were applied in modified form by the authors.
be related to the experimental mean residence time
These data were reformulated with dimensionless
(tM)G as follows:
numbers as FrG, WeG and ScG (Table 3) and were
fitted by the nonlinear least-squares method; they are
dG ∗ (1,s )
L H d,G lim restricted to the following ranges of operation: dP =
( µ1 )G = ( t M )G = − S→0 ds (44) 3.20 10-3 m, 21.36 ≤ ReG ≤ 92.56, 10-4 ≤ FrG ≤ 3.23
VSL lim G (1,s )
∗
10-3, 5.30 10-2 ≤ ScG ≤ 2.28 10-1 and 10-5 ≤ WeG ≤
S→0
8.30 10-4.
Development of this expression is given in Appendix Figs. 6, 8 and 10 show plots of Dax, KGL and kLS
D. as a function of ReG, FrG, ScG and WeG. Figs. 7, 9
The numerical procedure for optimization of and 11 contain parity plots of the results obtained
these parameters involved numerical inversion in the through the method applied in this work for each gas
Fourier domain followed by an optimization flow utilized in the three-phase operation vs those
subroutine (Cooley and Twkey, 1965; Box, 1965). results predicted from the correlations expressed by
The initial and optimized values of these three Eqs. 45, 46 and 47.

Brazilian Journal of Chemical Engineering, Vol. 20, No. 04, pp. 375 - 390, October - December 2003
382 J.D.Silva, F.R.A.Lima C.A.M.Abreu and A.Knoechelmann

Table 2: Initial and optimized values of the dispersion coefficient and mass
transfer parameters. QL = 0.50 10-6 m3 s-1 .

Gas - Phase Initial Optimized Objective

Flows Values Values Function
QG 106 Dax 105 KGL 104 kLS 102 Dax 105 KGL 104 kLS 102
F 104
(m3 s-1) (m2 s-1) (m s-1) (m s-1) (m2 s-1) (m s-1 (m s-1)
41.69 63.89 69.33 49.18 33.95 37.79 20.43 1.57
40.00 59.29 63.91 45.20 32.78 36.89 19.23 1.47
38.35 56.07 57.43 41.77 31.19 35.14 18.01 1.40
36.68 49.12 56.98 39.20 29.98 34.24 16.89 1.41
35.01 48.02 50.43 36.14 28.40 32.57 15.52 1.37
33.34 45.27 49.10 31.21 27.23 31.69 13.31 1.39
31.67 40.98 47.35 29.06 25.66 30.12 11.92 1.21
30.01 39.01 44.12 26.98 24.47 29.13 10.14 1.38
28.34 37.40 41.09 21.15 22.88 27.58 9.39 1.12
26.67 36.14 39.12 19.51 21.67 26.77 8.23 1.21
25.01 34.21 35.42 13.78 20.11 25.14 6.87 1.30
23.33 33.14 31.77 10.27 18.95 24.17 5.46 1.09
21.66 29.20 29.10 9.08 17.40 22.46 4.39 1.27
19.99 27.12 27.81 7.29 16.23 21.55 3.02 1.16
18.32 24.01 23.18 5.21 14.67 19.88 2.06 1.01
16.65 21.14 21.14 4.20 13.46 18.93 1.54 1.11
14.98 18.22 19.88 3.02 11.89 17.22 0.97 1.21
13.31 16.10 18.10 2.51 10.71 16.23 0.78 1.17
11.64 11.89 16.80 2.01 9.09 14.54 0.48 1.18
9.97 9.78 13.98 1.09 7.89 13.65 0.27 1.08

Figure 2: Concentration profiles for the methane gas tracer at the entrance and the
exit of the γ - Al2O3 bed in QG = 33.34 10-6 m3 s-1 and QL = 0.50 10-6 m3 s-1

Figure 3: Concentration profiles for the methane gas tracer at the entrance and
the exit of the γ - Al2O3 bed in QG = 18.32 10-6 m3 s-1 and QL = 0.50 10-6 m3 s-1
Brazilian Journal of Chemical Engineering
 Experimental Analysis and Evaluation of the Mass Transfer Process 383

Figure 4: Validation of the tracer concentration at the
exit of the γ-Al2O3 bed; ♦ results in gas and liquid
flows QG = 36.68 10-6m3 s-1 and QL = 0.5 10-6m3 s-1; 
results in parameters Dax = 2.98 10-4 m2s-1, KGL = 3.24
10-3 m s-1 and kLS = 1.68 10-1 m s-1
Figure 5: Validation of the tracer concentration at the
exit of the γ-Al2O3 bed; ♦ results in gas and liquid
flows QG = 14.98 10-6m3 s-1 and QL = 0.5 10-6m3 s-1; 
results in parameters Dax = 1.18 10-4 m2s-1, KGL = 1.72
10-3 m s-1 and kLS = 1.56 10-2 m s-1

Table 3: Correlations for axial dispersion and mass transfer parameters.

Correlations Statistical Results References

-5
(σ)Dax = 8.09 10
D ax = 1.67 10 − 6
( ReG )0.088 ( FrG ) 0.432 (45)
R = 0.9942
Stiegel and Shah (1977)

− 0.842 − 1.576 (σ)KGL = 7.60 10-5

K GL = 1.65 10−4 ( ReG ) ( WeG ) (46) Fukushima and Kusaka (1977)
R = 0.9945
(σ)kLS = 0.0672
k LS = 3.58 10−3 ( ReG ) (ScG )0. 317
1. 397
(47) Chou et al. (1979)
R = 0.9917

Figure 6: Dax vs (ReG)0.088, (FrG) 0.432 for the Figure 7: (Dax)Exp vs (Dax)Calc for the H2O/Ar – CH4/ γ -
H2O/Ar – CH4/ γ - Al2O3 system in trickle- Al2O3 system in trickle-bed regime. QG = (41.69 to
bed regime 9.97) 10-6 m3 s-1 and QL = 0.50 10-6 m3 s-1

Brazilian Journal of Chemical Engineering, Vol. 20, No. 04, pp. 375 - 390, October - December 2003
384 J.D.Silva, F.R.A.Lima C.A.M.Abreu and A.Knoechelmann

Figure 8: KGL vs (ReG)-0.842, (WeG) – 1.576 for the Figure 9: (KGL)Exp vs (KGL)Calc for the H2O/Ar – CH4/ γ
H2O/Ar – CH4/ γ - Al2O3 system in trickle-bed - Al2O3 system in trickle-bed regime. QG = (41.69 to
regime 9.97) 10-6 m3 s-1 and QL = 0.50 10-6 m3 s-1

Figure 10: kLS vs (ReG)1.397, (ScG) 0.317 for the

Figure 11: kLS, Exp vs kLS, Calc for the H2O/Ar – CH4/ γ -
H2O/Ar – CH4/ γ - Al2O3 system in trickle-
Al2O3 system in trickle-bed regime. QG = (41.692 to
bed regime
9.973) 10-6 m3 s-1 and QL = 0.50 10-6 m3 s-1

CONCLUSIONS to 7.89 10-5 m2 s-1, KGL = 37.79 10-4 m s-1 to 13.65

10-4 m s-1 and kLS = 20.43 10-2 m s-1 to 0.27 10-2 m s-1.
Based on the experimental and modeling studies
of this gas-phase trickle-bed systems the following
results were obtained: (i) estimation of parameters ACKNOWLEDGMENTS
Dax, KGL and kLS, (ii) validation of the model and (iii)
analysis of the behavior of the axial dispersion and The authors would like to thank CNPq (Conselho
gas-liquid and liquid-solid coefficients by new forms Nacional de Desenvolvimento Científico e Tecnológico)
of empirical correlations. for its financial support (process 141496/98-3).
The final values of the parameters were obtained
with values of the objective function, F = 1.08 10-4 to
1.57 10-4. Thus, the range of optimized values of the NOMENCLATURE
parameters obtained by the fitting between the
experimental and theoretical response and according a1(s) Function defined in Eq. 28
to validation tests are given as Dax = 33.95 10-5 m2 s-1 aGL Gas-liquid mass transfer area per unit

Brazilian Journal of Chemical Engineering

 Experimental Analysis and Evaluation of the Mass Transfer Process 385

column volume [m-1] R Radius of the catalyst particle [m]

aP Effective liquid-solid mass transfer area R(s) Function defined in Eq. 28
per unit column volume [m-1] ReG Reynolds number, ReG = VSG ρG dh / µG
CG,0 Input concentration of the gas tracer [kg m-3] Sh Sherwood number, Sh = kLS R / De
CG(z,t) Concentration of the gas tracer in the ScG Schmidt number, ScG = µG / ρG Dax
gaseous phase [kg m-3] t Time (s)
CL(z,t) Concentration of the CH4 tracer in the T Temperature of the system [ K ]
liquid phase [kg m-3] T(s) Function defined in Eq. 36
Cr (r,t) Concentration of the CH4 tracer in the solid tA Dimensionless time defined in Eq. 10
phase [kg m-3] (tM)G Mean residence time [s]
D(s) Determinant defined in Appendix C, Eq.C9 Vi∗ Function defined in Appendix C, i = 1, 2, 3
Di(s) Determinant defined in Appendix C, i = 1, VR Volume of the reactor [m3]
2, 3 VSG Superficial velocity of the gaseous phase
Dax Axial dispersion coefficient for the gas [m s-1]
tracer in the liquid phase [m2 s-1] VSL Superficial velocity of the liquid phase [m
De Effective diffusivity for the gas tracer in s-1]
the solid phase [m2 s-1] WeG Weber number, WeG = (VSG)2 ρG dh / σL
dh Equivalent diameter of the bed, dh = dP [16 W Catalytic mass, kg
(εex)2 / 9 π (1 - εex)2 ]1 / 3 [m] z Axial distance of the catalytic reactor [m]
Dp Diameter of the catalyst particle [m]
Dr Diameter of the reactor [m] Greek Letters
F Objective function
fi(s) Integration constants; i = 1, 2, 3 α Parameter defined in Eq.17, dimensionless
fe Partial wetting factor β Angle for the vertical inclination defined in
FrG Modified Froude number, FrG = ρG (VSG)2 / Eq. 7
dh (ρG g + δGL) γ Parameter defined in Eq.17, dimensionless
g Standard acceleration of gravity [m s-2] Γi Dimensionless concentrations of the gas,
GG Mass velocity of the gaseous phase [kg m-2s-1] liquid and solid, i = G, L, S
GL Mass velocity of the liquid phase [kg m-2s-1] Γi∗ Laplace domain concentrations of the gas,
H Solubility constant of Henry’s law, liquid and solid, i = G, L, S
dimensionless
δ(s) Function defined in Eq. 31
H(s) Function defined in Eq. 35
δGL Two-phase pressure [kg m-2 s-2]
Hd,G Dynamic gas holdup, dimensionless
Hd, L Dynamic liquid holdup, dimensionless εex Void fraction in the bed, dimensionless
HS Static liquid holdup, dimensionless η Radial distance in the catalyst particle,
dimensionless
i complex number − 1
κ Parameter defined in Eq. 17
J(s) Function defined in Eq. 35 λ Parameter defined in Eq. 18
Ki(s) Function defined in Eq. 31, i = 1, 2 λi Roots of the characteristic Eq. 32, i = 1, 2, 3
Ki Constants defined in Eq. 9, i = 1, 2 µL Viscosity of the liquid phase [kg m-1 s-1]
KA Adsorption equilibrium constant [m3 kg-1]
µG Viscosity of the gaseous phase [kg m-1 s-1]
KGL Overall gas-liquid mass transfer coefficient
ρG Density of the gaseous phase [kg m-3]
[m s-1]
kLS Liquid-solid mass transfer coefficient [m s-1] ρL Density of the liquid phase [kg m-3]
L Height of the catalyst bed [m] ρP Density of the particle [kg m-3]
P Pressure [Pa] ρLe Bed density [kg m-3]
PE∗ Modified Peclet number based on the σL Surface tension [kg s-2]
height of the catalyst bed
PE Peclet number based on the height of the
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QL Flow of the liquid phase [m3 s-1] Laurent, A., High-Pressure Trickle Bed Reactors:
r Radial distance in the catalyst particle bed [m] A Review, Industrial Engineering Chemical

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Ramachandran, P.A. and Smith, J., Dynamics Líquida em Leito Poroso, XXVIII Congresso
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Sci., 34, 75-91 (1979). (2000b).
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(1996). The Use of Large-Scale Computer Assisted
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Dinâmica de um Reator Trifásico a Leito Fixo Dudukovic, M.R., Evaluation of Trickle-Bed
Gás-Líquido-Sólido com Escoamento Reactors Models for a Liquid Limited Reaction,
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APPENDIX A d Pr∗ (1,s )

= Sh Γ∗L ( ξ,s ) − ( Sh − 1) Pr∗ (1,s ) ;
Eq. 21 was solved in the following manner: dη
(A4)
Pr∗ ( 0,s ) = 0
d 2 Γ∗r ( η,s ) 2 d Γ r ( η,s )
∗
2
+ = φ
 ( s )  Γ∗r ( η, s ) ;
dη2 η dη The solution of Eq. A3 with its boundary
(A1) conditions given by Eq. A4 is
2 s
 ( s )  = λ
φ
Sh Γ∗L ( ξ,s ) sen h  φ( s ) η
Pr∗ ( η,s) = (A5)
A change in variable in this equation and its
{
φ( s ) cosh φ
 ( s )  + ( Sh −1) sen h φ }
 ( s ) 
boundary conditions was made using the following
With the original variable Γ∗r (η, s), given by Eq.
ratio:
A2, the following equation was obtained:

Pr∗ ( η, s ) Sh Γ∗L ( ξ,s )

Γ∗r ( η, s ) = (A2) Γ∗r (1,s ) = (A6)
η  φ ( s ) cot gh φ
 ( s )  + ( Sh − 1) 

Using the above ratio Eq. A1 was transformed into:

APPENDIX B
d 2 Pr∗ 2
 ( s ) 
− φ Pr∗ ( η,s ) = 0 (A3)
Combining Eqs. 19 and 20 in the Laplace domain,
dη2

Brazilian Journal of Chemical Engineering, Vol. 20, No. 04, pp. 375 - 390, October - December 2003
388 J.D.Silva, F.R.A.Lima C.A.M.Abreu and A.Knoechelmann

dΓ∗G ( ξ,s ) 1 d Γ L ( ξ,s )

2 ∗
+ a1 ( s ) Γ∗G ( ξ,s ) = αΓ∗L ( ξ,s ) (B1) Γ∗G ( ξ,s ) = −
dξ PE∗ γ dξ 2
(B8)
1 d Γ L ( ξ,s ) dΓ∗L ( ξ,s ) κ d Γ L ( ξ,s ) ν ( s ) ∗
2 ∗ ∗
−κ = + + Γ L ( ξ,s )
PE∗ dξ 2 dξ γ dξ γ
(B2)
−γ Γ∗G ( ξ,s ) + ν ( s ) Γ∗L ( ξ,s ) dΓ∗G ( ξ,s ) 1 d Γ L ( ξ,s )
3 ∗
=−
Combination 1: the response in the gaseous phase
dξ PE∗ γ dξ 3
(B9)
was obtained as follows: isolating Γ∗L (ξ,s) from Eq.
B1 and then differentiating Γ∗L (ξ, s) twice with κ d 2 Γ∗L ( ξ,s ) ν (s) d Γ∗L ( ξ, s )
+ +
respect to ξ. γ dξ 2 γ dξ

1 d Γ G ( ξ,s ) a1 ( s ) ∗
∗
Eqs. B8 and B9 were introduced in to Eq. B1 to
Γ∗L ( ξ,s ) = + Γ G ( ξ,s ) (B3) obtain the following equation:
α dξ α

d Γ∗L ( ξ,s ) 1 d ΓG ( ξ,s ) a1 ( s ) dΓ G ( ξ,s )

2 ∗ ∗ d3Γ∗L ( ξ,s ) d 2 Γ∗L ( ξ,s )
= + (B4) + δ (s)
dξ α dξ2 α dξ dξ 3 d ξ2
(B10)
2
d Γ ∗
( ξ,s ) = 1 d 3
Γ∗G ( ξ,s ) + a1 ( s ) d 2
Γ∗G ( ξ,s ) d Γ∗L ( ξ,s )
L
(B5) − K1 ( s ) + K 2 ( s ) Γ∗L ( ξ,s ) = 0
dξ 2 α dξ 3 α dξ 2 dξ

Introducing Eq. B3, B4 and B5 in to Eq. B2, the

following equation for the methane gas tracer in the APPENDIX C
gaseous phase was found:
Formal solutions of Eqs. B6 and B10 were
d3Γ∗G ( ξ,s ) + δ d 2 Γ∗G ( ξ,s ) suggested by Ramachandran and Smith (1979), as
3
(s) follows:
dξ dξ 2
(B6)
3
dΓ∗G ( ξ,s )
− K1 ( s )
dξ
+ K 2 ( s ) Γ∗G ( ξ,s ) = 0 Γ∗G ( ξ,s ) = ∑ f ( s ) exp λ
i =1
i  ( s ) ; i

(C1)
where 3
fi ( s )
Γ∗L ( ξ,s ) = ∑ λ
 ( s ) − a ( s ) 
i =1
i 1
α  i ( s ) 
exp λ
δ ( s ) = a1 ( s ) − PE∗ κ  ;
 
In Eq. C1 the integration constants, fi (s), were
K1 ( s ) = a1 ( s ) κ + ν ( s )  PE∗ ; (B7)
calculated from the three boundary conditions given
in Eqs. 22 and 23, expressed in the Laplace domain.
K 2 ( s ) = αγ
 − a1 ( s ) ν ( s )  PE
∗
They were evaluated by the following system of
algebraic equations:
Combination 2: The response in the liquid phase
was obtained as follows: isolating Γ∗G (ξ, s) from Eq. f1 ( s ) + f 2 ( s ) + f3 ( s ) = 1 s (C2)
B2 and then differentiating Γ∗G (ξ, s) with respect to ξ.

{λ  1 ( s ) } f1 ( s ) + {λ

 1 ( s ) − a1 ( s )  λ1 ( s ) exp λ  2 ( s )} f 2 ( s ) + {λ
 2 ( s ) − a1 ( s ) λ 2 ( s ) exp λ  3 ( s ) − a1 ( s ) (C3)
 3 ( s ) } f3 ( s ) = 0
λ 3 ( s ) exp λ

Brazilian Journal of Chemical Engineering

 Experimental Analysis and Evaluation of the Mass Transfer Process 389

  λ1 ( s )    λ 2 ( s )  

 λ1 ( s ) − a1 ( s )  
 PE  
{
− 1  f1 ( s ) + λ
 2 ( s ) −a1 ( s ) 
 
 PE  
{
− 1  f 2 ( s ) + λ 3 ( s ) − a1 ( s )
(C4)
 λ3 ( s )   
 − 1  f 4 ( s ) = 0
 PE  

The system of algebraic equations given by Eqs. (C2), (C3) and (C4) was solved by Cramer’s method, so
determinants D(s) were defined by

 1 ( s ) , λ 2 ( s ) ,a1 ( s )  + T2 λ
D(s) = T1∗ λ  1 ( s ) , λ 2 ( s ) λ 3 ( s ) ,a1 ( s ) + T3 λ
 1 ( s ) , λ 2 ( s ) , λ 3 ( s ) ,a1 ( s )
∗ ∗
(C5)

where


 λ 2 ( s ) 
T1∗ λ
 1 ( s ) , λ 2 ( s ) ,a1 ( s )  =
   λ 2 ( s ) − a1 ( s ) 
 λ 2 ( s ) exp λ
 2 ( s ) 
  λ 2 ( s ) − a1 ( s )  P
− 1 
  E  (C6)
λ1 ( s )  
{  λ1 ( s ) − a1 ( s )  

 PE
− 1 
 

  λ2 (s )  
 1 ( s ) , λ 2 ( s ) , λ 3 ( s ) ,a1 ( s )  = λ1 ( s ) − a1 ( s )  λ1 ( s ) exp λ
T2∗ λ  1 ( s ) λ  2 ( s ) − a1 ( s )  − 1 
PE 
   (C7)
 λ2 (s ) 
 
{
− λ 2 ( s ) − a1 ( s )  
 P
− 1 
E  

T3∗ λ {
 1 ( s ) , λ 2 ( s ) , λ3 ( s ) ,a1 ( s )  = λ  3 ( s ) − a1 ( s )  λ 3 ( s ) exp λ
 {{
 3 ( s ) λ
 λ1 ( s ) − 1 
 1 ( s ) − a1 ( s )  
 PE




(C8)
λ 2 ( s )  
{
− λ 2 ( s ) − a1 ( s ) 

−1
PE   

Determinants D1(s), D2(s) and D3(s) are given by

D1 ( s ) = 1 s V1∗ λ
 2 ( s ) , λ 3 ( s ) ,a1 ( s )  (C9)

D2 ( s ) = 1 s V2∗ λ
 1 ( s ) , λ 3 ( s ) ,a1 ( s )  (C10)

D3 ( s ) = 1 s V3∗ λ
 1 ( s ) , λ 2 ( s ) ,a1 ( s )  (C11)

where

 λ 3 ( s ) 
 2 ( s ) , λ3 ( s ) ,a1 ( s )  = λ
V1∗ λ  2 ( s ) − a1 ( s )  λ
 3 ( s ) −a1 ( s )   P
− 1 λ 2 ( s ) exp λ
 2 ( s ) −
 E  (C12)
λ 2 ( s )  
 − 1 λ 3 ( s ) exp λ  3 ( s )  
 PE  

 λ1 ( s ) 
 1 ( s ) , λ3 ( s ) ,a1 ( s )  = λ
V2∗ λ  1 ( s ) − a1 ( s )  λ
 3 ( s ) −a1 ( s )    P
− 1 λ 3 ( s ) exp λ
 3 ( s ) −
 E  (C13)
λ 3 ( s )  
 − 1 λ1 ( s ) exp λ  1 ( s )
 
 P E  
Brazilian Journal of Chemical Engineering, Vol. 20, No. 04, pp. 375 - 390, October - December 2003
390 J.D.Silva, F.R.A.Lima C.A.M.Abreu and A.Knoechelmann

 λ 2 ( s ) 
 1 ( s ) , λ 2 ( s ) ,a1 ( s )  = λ
V3∗ λ  1 ( s ) − a1 ( s )  λ
 2 ( s ) −a1 ( s )   P
− 1 λ1 ( s ) exp λ
 1 ( s ) −
 E  (C14)
λ1 ( s )  
 − 1 λ 2 ( s ) exp λ  2 ( s ) 
 PE  

The integration constants are obtained as

Di ( s )
fi ( s ) = , (i = 1, 2, 3) (C15)
D (s)

APPENDIX D development is given in Appendix C. The parameter

Variables V1∗, V2∗ and V3∗ in the transfer function
are functions of λi(s) → i = 1, 2, 3 and a1(s), while
variables T1∗, T2∗ and T3∗ in D(s) are also functions
of λi(s) → i = 1, 2, 3 and a1(s). A detailed
estimation technique by the method of moments was
developed by Van Der Laan (1957). This technique
was used for parameters that are functions of the
Laplace transform variable (s → 0), according to the
procedure below.

limG∗ (1,s) =
S→0
1
{
lim V∗ ( λ2 ( s ) , λ3 ( s) ,a1 ( s ) ) exp lim λ1 ( s)  + lim V2∗ ( λ1 ( s) , λ3 ( s) ,a1 ( s) ) exp lim λ2 ( s)  +
lim D( s) S→0  1 S→0  S→0  S→0 
(D1)
}
S→0


S→0 
( S→0
)
lim V3∗ λ1 ( s) , λ 3 ( s ) ,a1 ( s ) exp lim λ3 ( s) 


lim D ( s ) = lim T1∗ λ

 1 ( s ) , λ 2 ( s ) ,a1 ( s )  + lim T2 λ
∗
 1 ( s ) , λ 2 ( s ) , λ 3 ( s ) ,a1 ( s ) +
S→0 S→0 S→0 (D2)
 1 ( s ) , λ 2 ( s ) , λ 3 ( s ) ,a1 ( s ) 
lim T3∗ λ
S→0

The term referring to the differentiation is given by the following equation:

dG∗ (1,s )
lim = lim A1 ( s ) + lim A 2 ( s ) + lim A3 ( s ) (D3)
S→0 ds S→0 S→0 S→0

where

1  d dD ( s )
lim A1 ( s ) =  lim  V1 ( λ 2 ( s ) , λ 3 ( s ) ,a1 ( s ) ) exp λ1 ( s )  lim D ( s ) − lim
∗
2
S→0 lim  D ( s )   S→0 ds S→0 S→0 ds
(D4)
S→0
lim  V1∗ ( λ 2 ( s ) , λ3 ( s ) ,a1 ( s ) ) exp λ1 ( s ) 
S→0 
}
lim A 2 ( s ) =
S→0
1
lim  D ( s ) 
{lim
2 S→0
d  ∗
ds 
V2 ( λ1 ( s ) , λ3 ( s ) ,a1 ( s ) ) exp λ 2 ( s )  lim D ( s ) − lim
 S→0
dD ( s )
S→0 ds
(D5)
S→0
lim  V2∗
S→0 
( λ1 ( s ) , λ3 ( s ) ,a1 ( s ) ) exp λ 2 ( s )}

lim A3 ( s ) =
S→0
1
lim  D ( s ) 
{lim
2 S→0
d  ∗
ds 
V3 ( λ1 ( s ) , λ 2 ( s ) ,a1 ( s ) ) exp λ 3 ( s )  lim D ( s ) − lim
 S→0
dD ( s )
S→0 ds
(D6)
S→0
lim
S →0
 V3∗ V3∗
 ( λ1 ( s ) , λ 2 ( s ) ,a1 ( s ) ) exp λ3 ( s )}
As the differentiations of the determinants are very lengthy, they are not shown.
Brazilian Journal of Chemical Engineering