Determination of Mass Transfer Resistances of Fast Reactions

in Three-Phase Mechanically Agitated Slurry Reactors

Ilias K. Stamatiou and Frans L. Muller
Institute of Process Research and Development (iPRD), University of Leeds, Leeds, LS2 9JT, U.K.

DOI 10.1002/aic.15540
Published online November 11, 2016 in Wiley Online Library (wileyonlinelibrary.com)

A methodology for the determination of mass transfer resistances of fast reactions in three-phase mechanically agitated
slurry reactors under the reaction conditions is presented. The mass transfer resistances affect significantly the overall
mass transfer rate, the design equation and consequently the scale up of the reactor. There is not established methodol-
ogy to separate the mass transfer resistances under reaction conditions by changing catalyst loading and manipulating
the process variables, pressure and agitation speed. This allows to avoid the use of different catalyst particles and give
the chance to calculate the mass transfer resistances without caring about the type of catalyst. We calculate each mass
transfer resistance under conditions which do not allow to neglect any of the resistances. It is shown that the level off
of mass transfer rate which is developed in the plot of mass transfer rate against agitation speed plots is not enough to
determine the limiting regime. The hydrogenation of styrene over Pd/C (5% catalyst content) is used as case study to
demonstrate the methodology. V C 2016 American Institute of Chemical Engineers AIChE J, 63: 273282, 2017

Keywords: mass transfer, reaction kinetics, reactor analysis

Introduction
Gas-liquid-solid three phase reactors are of great impor-
tance in pharmaceutical and fine chemical industry. The
mechanically agitated slurry reactors are the most common
type of three phase reactors which are used within these
industries.1
During the three-phase reactions a number of mass transfer
processes need to take place before the surface catalytic reac-
tion: (a) gas-liquid mass transfer, (b) liquid-solid mass trans-
fer, and (c) the combined internal pore diffusion and the
surface chemical reaction. Each of the mass transfer processes
and the intrinsic reaction rate affect the overall process rate in
different extent.1,2 The design of three phase reactors requires
the determination of the mass transfer coefficients and the
reaction rate constant. The determination of mass transfer
coefficients becomes even more important when the reaction
rate constant and external mass transfer is of comparable mag-
nitude. This happens in the case of fast chemical reactions. In
fast chemical reactions, even if intense mixing conditions take
place, the external mass transfer processes are not faster than
the surface chemical reaction.
Many researchers have used several methods to separate the
effect of each of the mass transfer coefficients. Currently,
there is not any established methodology for the separation of
each of the mass transfer coefficients and the reaction rate con-
stant (a) under the reaction conditions, (b) without changing
the size of the catalyst, (c) under conditions which do not
Correspondence concerning this article should be addressed to I. K. Stamatiou
at pmist@leeds.ac.uk.
C 2016 American Institute of Chemical Engineers
V gen pressure, instead of changing catalyst size. We apply the
allow to neglect any of the rate, and (d) without needing to use
low substrate concentration. Many researchers have studied
the hydrogenations of unsaturated organic compounds by
varying the hydrogen partial pressure but they have not manip-
ulated the overall mass transfer resistance against the square
root of hydrogen concentration in gas-liquid interface, CH2 ;i =
MTRH2 vs. CH2 ;i 0:5 .3,4 Tiwari et al.5 used the plot of CH2 ;i =
MTRH2 vs. CH2 ;i to calculate the reaction rate constant of the
surface reaction of 3,4-dimethoxyphenone, but they assumed
negligible external mass transfer resistance in their model.
Joshi et al.6 used also these kind of plots to calculate the reac-
tion constants of homogeneously catalysed styrene hydrogena-
tion. The gas-liquid mass transfer coefficient is usually
determined using the dynamic physical absorption meth-
od.2,3,7,8 Cordova and Harriott9 and Gholap et al.10 calculated
gas-liquid mass transfer coefficient and the liquid-solid mass
transfer coefficient by changing catalyst loading and using dif-
ferent size of catalyst particle under reaction conditions. The
drawback of varying catalyst size is the requirement of shell
type catalyst to ensure interparticle diffusion does not depend
on catalyst size. Ruether and Puri11 separated the reaction rate
constant from the mass transfer resistances but they used a
very low concentration of substrate to obtain a first-order reac-
tion rate with respect to substrate concentration. In this case
the limiting reactant is the substrate, something that occurs in
industrial hydrogenators only during the end of the batch
reaction.
The objective of this article is to build a methodology for
the separation of mass transfer effects in three phase processes
in mechanically agitated hydrogenators under the reaction
conditions by manipulating the agitation speed and the hydro-

AIChE Journal January 2017 Vol. 63, No. 1 273

 Table 1. Mass Transfer Resistances
Description Expression Definition Figure 1. Hydrogen dissociative chemisorption.
External mass Resistance of
1
transfer resistances gas-liquid XH2 ;i2L KL a
interface
Resistance of 1 PH 2
1
liquid-solid XH2 ;L2S KS aS W c MTRH2 5 1 1 1
 (8)
interface
V L
KL a 1 KS aS W c 1 ek0 Wc
HE
V L obs VL
Resistance of
internal catalyst XH2 ;R 1
From Eq. 8, we realize that the three components at the denomi-
0 Wc
ekobs
pore structure and V L

surface chemical reaction nator act as barriers to the MTR, the higher they are the slower
the rate. In an analogy to the Ohms law, the components of the
concept of mass transfer resistance adopting the consideration denominator are called resistances. The denominator represents
of Levenspiel12 about heterogeneous reactions. Therefore, we the overall mass transfer resistance, XH2 ;tot , on the hydrogenation
assume that mass transfer processes and chemical reaction process. Table 1 gives the definition of each of the resistances.
take place in series. By manipulating appropriately Eqs. 15 and 7, we conclude
to the following expressions for CH2 ;i , CH2 ;L , and CH2 ;S ,
" #
Theoretical Background 1 1 1
Mass transfer in hydrogenation process CH2 ;i 5MTRH2  1 1 (9)
K L  a K S  aS  W VL
c 0  Wc
e  kobs VL
The overall process of the styrene hydrogenation consists of " #
four steps which take place in series1,9,1316: 1 1
1. Absorption of H2 into g-l interface from bulk gas phase CH2 ;L 5MTRH2  1 (10)
K S  aS  W
VL
c 0  Wc
e  kobs VL
  1
PH2 ;G PH2 ;i CH2 ;S 5MTRH2  (11)
MTRH2 ;1 5KG  a  HE  2 (1) e  kobs  W
0 c
HE HE VL

2. Diffusion of H2 into liquid phase from g-l interface To express hydrogen concentration on the external catalyst
  surface, CH2 ;S , as a function of the hydrogen concentration in
MTRH2 ;2 5KL  a  CH2 ;i 2CH2 ;L (2) gas-liquid interface, CH2 ;i , we introduce the factor b: Factor b
is defined as the ratio between XH2 ;R and XH2 ;tot .
3. Diffusion of H2 from liquid phase to particle external
CH2 ;S 5b  CH2 ;i (12)
surface
XH2 ;R
Wc   b5 (13)
MTRH2 ;3 5KS  aS  CH2 ;L 2CH2 ;S (3) XH2 ;tot
VL

Kinetics of surface catalytic reaction

4. Diffusion of H2 through particle pore structure and
The surface catalytic reaction can be broken down into the
chemical reaction on catalyst surface, assuming first-order
elementary steps. Figures 1 and 2 illustrate the dissociative
reaction with respect to H2
and molecular chemisorption onto catalyst surface, assuming
Wc that the substrate and hydrogen do not compete for the same
0
MTRH2 ;4 5e  kobs   CH2 ;S (4) catalyst site. Figure 3 illustrates the surface chemical reaction
VL
which is the rate determining step.12,19,20
In the case of pure hydrogen or slightly soluble gases, it is 1. Dissociative and molecular chemisorption onto the catalyst
unlikely the absorption of H2 to be the limiting step. As a surface
result it is neglected and the concentration of H2 at the g- A. Hydrogen dissociative chemisorption2125
l interface is considered to be in equilibrium with the gas At the equilibrium,
phase pressure of hydrogen based on the Henrys law.15,17 C2H2M1 q
KH 5 ) C H2M1 5 KH  CH2;S  CM1 (14)
PH2 5HE  CH2 ;i (5) CH2;S  C2M1
Under the range of pressure and temperature we used, the B. Molecular chemisorption of unsaturated organic com-
Henry constant, HE , is calculated by the correlation which is pound
described by Eq. 6 where HE in Mpa, T in K and PH2 in Pa.18 At the equilibrium,
4815:6
LnHE 5122:32 217:5  LnT 11:4  1027  PH2 (6)
T
Considering that the process reaches steady state conditions
fast, the four steps take place under the same rate. The overall
rate is determined by the slowest step.
MTRH2 ;1 5MTRH2 ;2 5MTRH2 ;3 5MTRH2 ;4 5MTRH2 (7)
From Eqs. 15 and 7, we conclude to the expression of the Figure 2. Molecular chemisorption of unsaturated
overall mass transfer rate, organic compound.

274 DOI 10.1002/aic Published on behalf of the AIChE January 2017 Vol. 63, No. 1 AIChE Journal
 Figure 3. Surface chemical reaction.

Table 2. Term Dependency on Process Variables and Catalyst Concentration

Hydrogen Stirrer Catalyst
Concentration, Speed, Concentration, Temperature,
Wc
CH2 ;i N VL T
XH2 ;i2L X  X 
XH2 ;L2S X   
XH2 ;R    
1
eko0 CR2CH5CH2;S p
1  X X 
CH ;i
2

b    

CP 1
KR 5 ) CP 5KR  CRCH5CH2;S  C2M2 (15) eko0 CR2CH5CH2;S p
1 WV c
CRCH5CH2;S  C2M2 XH2 ;R bCH ;i
2
L
b5 5
XH2 ;tot XH2 ;tot
2. Chemical reaction on catalyst surface and desorption of p
1
product from catalyst surface. p eko0 CR2CH5CH2;S V  Wc
 CH2 ;i
L
The rate of surface chemical reaction is, b5 (19)
XH2 ;tot
2R0H2 5e  k0  CP  CH2M1
Table 1 gives the definition of each of the resistances. Table 2
Substituting the expressions of HM1 and P, illustrates which of the terms of Eq. 18 change with respect to
q the process variables (N, CH2 ;i , T) and catalyst concentration.
2R0H2 5e  ko0  CR2CH5CH2;S  CH2;S (16)
p Methods
Where, ko0 5k0  KR  KH  CM1  C2M2
Materials
M1, M2 5 Catalyst active sites
Methanol 99.9%, styrene 99%, decane 99%, which were
Despite the reaction rate law that is described in Eq. 16, we purchased from Sigma Aldrich, were used as solvent, sub-
have assumed a first-order reaction with respect to the surface strate, and internal standard, respectively. Compressed pure
concentration of hydrogen, CH2 ;S , and zero order with respect hydrogen (UN: 1049) was purchased from BOC. 5% Palladi-
to the surface concentration of unsaturated organic compound, um on activated carbon (Type 87L) was purchased from John-
CR2CH5CH2;S . To take into account the reaction rate law which son Matthey. Table 7 summaries the physical properties of
is described in Eq. 16, we need to introduce an appropriate liquid and gas phase.
expression of the observed reaction constant of the surface
reaction, k0obs . Hydrogenation of styrene
0
 VL  MTRH2 ;4 5e  kobs  Wc  CH2 ;S p We chose the hydrogenation of styrene as case study to
 2Wc  R0H2 5Wc  e  ko0  CR2CH5CH2;S  CH2;S illustrate the suggested methodology. Experiments were per-
0
 VL  MTRH2 ;4 52Wc  RH2 formed in a 0.6 L batch stirred autoclave reactor (Parr Instru-
0 1 ment Company, USA), equipped with two 458 pitched turbine
kobs 5ko0  CR2CH5CH2;S  p type impellers. The diameter of the vessel is 6.5 cm and the
CH2;S
diameter of the impellers is 3.5 cm. One impeller was located
near the bottom and the second impeller positioned near the
We substitute CH2;S from Eq. 12,
0 1
kobs 5k0o  CR2CH5CH2;S  p (17)
b  CH2 ;i
0
Substituting the expression of kobs to Eq. 8 and rearranging,
we conclude to the following equation which describes the
overall mass transfer resistance of the hydrogenation process,
XH2 ;tot .
CH2 ;i 1 1 1
5 1 1
MTRH2 KL  a KS  aS  W
VL
c
e  ko
0 C
R2CH5CH2;S
 p
1
W
VL
c
bCH2 ;i

(18)
0
We substitute the expression of kobs to XH2 ;R and we rewrite
the expression of factor b. Figure 4. Total consumption of hydrogen volume.

AIChE Journal January 2017 Vol. 63, No. 1 Published on behalf of the AIChE DOI 10.1002/aic 275

Figure 5. Experimental set-up.
surface of the liquid to pull reactant gas down to the liquid
phase. The reactor was used in continuous flow with respect to
hydrogen. Reaction was monitored by measuring the con-
sumption of hydrogen using a mass flow controller in the inlet
of the reactor. Figure 4 illustrates typical accumulative con-
sumption curves of hydrogen in several agitation speeds. The
mass flow controller was set to keep the reactor pressure con-
stant. Pressure transducer is used to monitor pressure. The
temperature of reaction mixture is maintained at the desired
value by using an automatic temperature control. Figure 5
illustrates the experimental set-up. Table 3 gives the operating
conditions of the reactor and Table 4 summaries the design
characteristics of the reactor. The ratio between liquid and gas
phase, VL/VG, was about 1/2.
Results and Discussion
Separation of mass transfer resistances
Separation of XH2 ;i2L from XH2 ;L2S and XH2 ;R
The initial mass transfer rate is independent of styrene con-
centration. We rewrite Eq. 18 as below,
0 1
CH2 ;i 1 1 1 A  VL
5 1@ 1 (20)
MTRH2 KL  a KS  aS e  ko0  p
1 Wc
bCH2 ;i
If one observes the initial MTRH2 at different catalyst loading,
Wc , keeping same the rest of the variables (N, CH2 ;i , and T)
and plots XH2 ;tot vs. VL =Wc , then the intercept of the graph will
be equal to the 1/KLa. Repeating the same procedure at differ-
ent agitation speed, the 1/KLa can be calculated for several
agitation speeds. Figure 6 illustrates the results. Each subgraph
corresponds to a set of different experiments under the same
stirrer speed. In each subgraph, the reaction temperature and
Table 3. Reactor Operating Conditions
Temperature Pressure Agitation Speed
T (8C) P (MPa gauge) N (rpm)
32 0.21.0 2001200
276 DOI 10.1002/aic Published on behalf of the AIChE
the concentration of hydrogen in gas-liquid interface are kept
constant.
The catalyst concentrations varied from 0.05 g cat/L solvent
to 1.5 g cat/L solvent while each experiment was repeated
three times. The correlation coefficient, r, was calculated to
measure the linear association between the experimental data
of XH2 ;tot and VL =Wc at each agitation speed. To check if the
linear regression models fit the data, the coefficient of determi-
nation, r2, was calculated. The model residuals analysis
showed lack of any particular pattern. The confidence intervals
for the models parameters were also calculated and they are
presented in Table 5. Figure 7 summaries the results. The
most significant effect of agitation speed on XH2 ;i 2 L of agita-
tion speed was observed between 200 and 500 rpm. From
500 rpm up to 900 rpm the agitation speed affects XH2 ;i2L less.
Taking into account the 95% confidence intervals of the calcu-
lated parameters, a plateau is developed at agitation speed
higher than 800 rpm. The plateau could have been reached
because of impeller overloading that affects its ability to dis-
perse all the gas supplied.
Separation of XH2 ;R from XH2 ;i2L and XH2 ;L2S
We rewrite Eq. 18 as below,
CH2 ;i 1 1 1
5 1 1  C0:5
H2 ;i (21)
MTRH2 KL  a KS  aS  W c
e  ko  b20:5  W
0 c
V L V L
By changing the hydrogen pressure in the reactor vessel, one is
able to manipulate the concentration of hydrogen in gas-liquid
interface. We conducted experiments at several hydrogen pres-
sures observing the initial MTRH2 . Each experiment took place
under same (a) stirrer speed, (b) temperature, and (c) catalyst
concentration. It should be noticed that the experiments took
place under conditions where XH2 ;R > XH2 ;i2L and XH2 ;R >
XH2 ;L2S . This is because we need the chemical reaction to be
the limiting regime. Otherwise gas to liquid or liquid to solid
mass transfer is the limitingpregime
of the process, resulting in
the XH2 ;tot independence of CH2 ;i . This independence does not
p
allow us to calculate the factor of CH2 ;i in Eq. 21.
We calculated the total mass transfer resistance
(XH2 ;tot 5CH2 ;i =MTRH2 ) at each hydrogen concentration. The
plot of XH2 ;tot with respect to C0:5 H2 ;i is distinguished in two dif-
ferent regions (Figure 8a). Both regions have constant slopes,
one higher than the other and constant intercepts. This indi-
cates that the factor of C0:5H2 ;i and the external mass transfer
resistances are constant in the range of each region. Therefore,
one is able to calculate the XH2 ;R =C0:5
H2 ;i term by applying linear
regression in the data of each region.
The experiments took place using one type of impellers
(two 458 pitched turbine type impellers) and one experimental
set-up which is shown in Figure 5 and its details are given in
Table 4. Therefore, we cannot extract conclusions if the two-
region behavior is case specific or not.
Table 4. Summary of Reactor Design Characteristics
Reactor characteristics
Reactor diameter, DR [m] 6.5 1022
Reactor volume, VR [m3 ] 6 1024
Impeller diameter, Dim [m] 3.5 1022
Number of impeller blades 4
Height of the blade, H [m] 8 1023
Number of impellers 2
Impellers distances from 3 1023 and 5.4 1022
the vessel bottom, [m]
January 2017 Vol. 63, No. 1 AIChE Journal
 Figure 6. Mass transfer resistance against catalyst concentration reciprocal at several agitation speeds.

Once the XH2 ;R =C0:5

H2 ;i term has been calculated, the XH2 ;R at XH2 ;tot . Figure 9 illustrates the steps of the procedure of
0.2 MPa, 1200 rpm and 0.05 g catalyst/L solvent is calculated. calculations.
Given the calculated XH2 ;R and the value of XH2 ;tot under the In this point, we need to notice that if the process is limited
same conditions (0.2 MPa, 1200 rpm and 0.05 g catalyst/L sol- by the surface chemical reaction, the slope of XH2 ;tot vs.
p
vent), the factor b is calculated. CH2 ;i should be nonzero. Otherwise gas to liquid or liquid to
From values of the factor b and the XH2 ;R p at
0.2 MPa, solid mass transfer is the limiting regime of the process. Figure
1200 rpm and 0.05 g catalyst/L solvent, the term CH2 ;i =e  ko0 8b illustrates this fact, at 1200 rpm and 0.05 g catalyst/L sol-
p vent (Case 1), XH2 ;tot depends on square root of hydrogen con-
is calculated. We have already noticed that the term CH2 ;i =e
ko0 is independent of agitation speed. The factor b depends on centration. Conversely, at 900 rpm and 0.125 g catalyst/L
agitation speed, resulting in XH2 ;R dependence on agitation solvent (Case 2), XH2 ;tot is independent of hydrogen concentra-
p tion. Figure 10 illustrates the contribution of each individual
speed. Using Eq. 19 and the value of the term CH2 ;i =e  ko0
mass transfer resistances for the Case 1 and 2.
the square root of factor b is calculated at agitation speeds The decreasing slope of the plot of XH2 ;tot with respect to
from 200 to 1200 rpm and in given catalyst concentration. C0:5
H2 ;i indicates that the factor b also decreasing. This means
Once we have got the factor b at any agitation speed, we are that the external mass transfer resistance increases from
able to calculate XH2 ;R at any agitation speed. The resistance Region 1 to Region 2. This is also obvious from the increased
of liquid-solid interface, XH2 ;L2S is calculated for that particu- intercept. Taking into account that the density and surface ten-
lar pressure range by subtracting XH2 ;i2L and XH2 ;R from sion of the liquid phase are practically constant between 0.3
and 1.1 MPa, the gas-liquid mass transfer coefficient can be
Table 5. Linear Regression Results of XH2 ;R Against VL =Wc considered constant.2 The increase of external mass transfer
in Several Agitation Speeds and 95% Confidence Interval of resistance may be caused by changes of the hydrodynamics
Estimated Parameters patterns due to the increase of pressure.
95% Confidence
interval of
estimated resistances
Slope Slope
N Intercept (min g cat Intercept (min g cat
(rpm) (min) L sol21 (min) L sol21
200 1.3581 0.0776 60.0277 60.0098
300 0.9072 0.0717 60.0887 60.0181
400 0.5581 0.0334 60.0081 60.0033
500 0.2986 0.0265 60.0110 60.0035
600 0.2635 0.0246 60.0173 60.0075
700 0.2348 0.0356 60.0166 60.0059
800 0.1566 0.0409 60.0207 60.0031
900 0.1133 0.0436 60.0142 60.0022
1000 0.1523 0.0255 60.0138 60.0024 Figure 7. Mass transfer resistances against agitation
1200 0.1909 0.0218 60.0472 60.0076
speed using 0.125 g catalyst/L solvent.

AIChE Journal January 2017 Vol. 63, No. 1 Published on behalf of the AIChE DOI 10.1002/aic 277
Figure 8. Mass transfer resistance against square root of hydrogen concentration in gas-liquid interface (left a, right b).

Figure 7 summarizes the separated mass transfer resistances

with respect to agitation speed. XH2 ;L2S presents the most sig-
nificant decrease between 300 and 400 rpm indicating that the
suspension speed lies on that range. A bump of XH2 ;L2S takes
place between 700 and 900 rpm. This may happen because at
700 rpm the stirrer starts pumping large gas volumes which
make the density of the gas-liquid mixture to decrease and to
cause the formation of gas cavities behind the stirrer blades.
This decrease of density and the formation of gas cavities lead
to a decrease of the power input with respect to the power
input into a pure liquid at the same agitation speed.2629 In
other words, the gassed system needs higher agitation speed to
have the same power input as the ungassed. Apart from the
bump, the XH2 ;L2S shows the same trend as XH2 ;i2L , reaching
a plateau.
Consequently, the mass transfer resistances are independent
of agitation speed after a critical value of agitation speed.
Therefore, the limiting regime of fast three-phase reactions
cannot be ensured just by observing the plateau of mass trans-
fer rate against agitation speed plots. This is because the pla-
teau can be due to either the external mass transfer resistances
or chemical reaction rate. Conversely, the chemical reaction
rate regime is ensured if we calculate each resistance and we
ascertain that the highest resistance is XH2 ;R .

Correlations
Gas-Liquid Mass Transfer Coefficient, KL  a. Several
correlations have been developed for the calculation of the
gas-liquid mass transfer coefficient. We used the classical cor-
relation based on the theory of isotropic turbulence using the
power consumption per liquid volume and the superficial gas
velocity to compare our experimental data.27,3035
 a1
P
KL  a5B1   ubsg1 (22)
VL
The power consumption in an ungassed vessel is correlated by
using the power number, Np, and the impeller Reynolds num-
ber, Reim.27,36 Figure 9. Steps of calculation of XH2 ;R and XH2 ;L2S .

278 DOI 10.1002/aic Published on behalf of the AIChE January 2017 Vol. 63, No. 1 AIChE Journal

Figure 10. Mass transfer resistances at 900 rpm, 0.125
g catalyst/L solvent and at 1200 rpm, 0.05 g
catalyst/L solvent.
P Substituting Eq. 24 to Eq. 22 and taking into account that
NP 5 (23)
qL  N 3  D5im
Once the impeller Reynolds number has been calculated the
power number is approximated by using appropriate graphs of
Np with respect to Reim. We used the graph which is developed
by Bates et al.37 In the case of 458 pitched turbine type impel-
lers the power number is constant for impeller Reynolds num-
ber higher than 103. The impeller Reynolds number of our
system is ranged from 6405 to 38,433, so we considered the
power number constant for our application. The power number
when more than one impellers are used can be approximated
as the power number of single impeller multiplied by the num-
ber of impellers (NP;n 5n  NP;1 ).38
Rearranging Eq. 23 with respect to power consumption and
dividing by the liquid volume VL, we conclude to Eq. 24.
P n  NP;1  qL  D5im 3
5 N (24)
VL VL
Using the same vessel and configuration of stirrers, the same
volume of liquid and under conditions which ensure constant
density of liquid phase the n  NP;1  qL  D5im =VL term can be
considered constant.
During the experiments the superficial velocity of hydrogen
was being determined by the consumption rate of hydrogen
because of the chemical reaction. We plotted the superficial
velocity of the hydrogen against the agitation speed. From
Figure 12. Summary of KL  a correlation results.
AIChE Journal January 2017 Vol. 63, No. 1 Published on behalf of the AIChE
Figure 11. Hydrogen superficial velocity against stirrer
speed.
Figure 11 one realizes that the superficial velocity of hydrogen
is practically constant.
the superficial velocity of hydrogen is constant,
KL  a5B  N 3a1 (25)
1 1
5  N 23a1 (26)
KL  a B
 a
Where, B5B1  ubsg1  n  NP;1  qL  D5im =VL 1
By applying nonlinear regression analysis, the exponent a1
and the constant term B were approximated. Figure 12 summa-
rizes the results. The exponent a1 which is calculated from our
data is equal to 0.47. Several researchers have reported the expo-
nent a1 for their systems to be between 0.3 and 0.65, see Table 6.
This means that the behavior of our system, with respect to
KL  a, is in agreement with the results presented in the literature,
justifying the way which we used to calculate the KL  a.
Liquid-Solid Mass Transfer Coefficient, KS  aS . In the
case of liquid-solid mass transfer coefficient we used the well-
known equation which correlates the Sherwood number with
Reynolds and Schmidt number for forced-convection mass
transfer from single spheres.39,40
 m
Sh521A  Rep  Scn (27)
To calculate the Reynolds number an appropriate expression
of velocity is required. That expression is given from Kolmo-
goroffs theory of isotropic turbulence which suggests that the
DOI 10.1002/aic 279
 Table 6. Values of Exponent a1 Proposed by Different
Table 7. Summary of Physical Properties of Liquid and Solid
Workers
Phase
Reference a1
Physical property Value
47
Robinson and Wilke 0.40
CH3OH density,54 qL [Kg=m3 ] 776.9
Linek et al.48 0.65
(P 5 0.3 Mpa to 1.1 Mpa)
Linek et al.49 0.59
CH3OH dynamic viscosity, lL [Kg=m  s] 4.98 1024
Chandrasekharan and Calderbank50 0.56
(T 5 328C)
Riet51 0.4
Diffusion coefficient of H2CH3OH 19:2  1028
Karimi et al.33 0.6
system,55 D [m2/min]
Yawalkar et al.52 0.47
Particle density, qp [Kg=m3 ] 2100
0.4
Particle diameter, dp [m] 20 1026
0.54
Figueiredo and Calderbank35 0.30.6
R. V. Chaudhari53 0.63

ungassed. Our reactor system can be considered as ungassed

up to 600 rpm and gassed for agitation speeds higher than
600 rpm. If one observes the XH2 ;L2S vs. N, it is clear that the
turbulent velocities are a function of only (a) the rate of energy XH2 ;L2S at 600 rpm and 1000 rpm is almost the same. Because
dissipation and (b) the kinematic viscosity of the fluid.41 of that, we assumed that the power input at 600 rpm and
The Reynolds number of particle, Rep , is defined as, 1000 rpm is the same. In other words, we assumed that the
dp4 dp4  q3L higher agitation speed has compensated the effect of gassing.
Rep 5  5  (28) Therefore, we did not take into account the interval from
v3L l3L
700 rpm to 900 rpm at the correlations.
The average energy dissipation rate per mass unit in the stirred By applying nonlinear regression analysis to Sh22=Sc1=3
tank is given by the Eq. 29.27 vs. Rep, the exponent m and the constant term A were approxi-
mated. Figure 13 summarizes the results. The exponent m
P
  aver 5 (29) which calculated from our data is equal to 0.46. That value
qL  p=4  D2im  H agrees well with the classical Frossling equation12,43,44 in
Substituting the expression of power input, P, to Eq. 29, which the exponent of particle Reynolds number is 1/2.
Gholap et al.10 and Teshima and Ohashi39 have reported a
n  NP;1  qL  D5im lower exponent of particle Reynolds number equal to 0.41
  aver 5  N3 (30)
qL  p=4  D2im  H while Sano et al.45 reported an exponent of particle Reynolds
number equal to 0.25 for agitated vessels and bubble columns.
Therefore, the Reynolds number of particle, Rep , is expressed In our system the constant term A equals 1.86. In the case of
as, steady state diffusion in a stagnant fluid, the Sherwood number
dp4  q3L 4 3 equals 2. The term A indicates the contribution of the forced
n  NP;1  D3im dp  qL 3
Rep 5  5  N (31) convection to the mass transfer. High values of A indicates
l3L p=4  H l3L high contribution of forced convection to the mass transfer.
To approximate the exponent of particle Reynolds number, we Miller46 has reported the A equals 1.1 for mass transfer from
set the Schmidt number exponent to 1/3 as this is the most fre- fixed solid spheres in agitated vessels. This is in agreement
quent value in the literature.42 with our results if one thinks that the contribution of forced
We have already mentioned that the gassed system needs convection in a system of free moved spheres should be higher
higher agitation speed to have the same power input as the than the contribution of fixed spheres. This means that the

Figure 13. Summary of KS  aS correlation results.

280 DOI 10.1002/aic Published on behalf of the AIChE January 2017 Vol. 63, No. 1 AIChE Journal
behavior of our system, with respect to KS  aS , is in agreement NP = power number
with the results presented in the literature, justifying the way n= number of impellers
PH2 = pressure of Hydrogen, Pa
which we used to calculate the KS  aS . P= power input, J/min
q ND2
Reim 5 L l im = Reynolds number of impeller
Conclusion L
dp4 q3L
Rep 5 l3L
= Reynolds number of particle
The mass transfer resistances in a three-phase mechanically
agitated slurry reactor can be calculated by changing catalyst R0H2 = reaction rate based on unit catalyst mass,
loading and manipulating only the agitation speed and the kmol H2 =kg catalyst  min
pressure of hydrogen. This allows to avoid the use of different r, = r 2 5 correlation coefficient, coefficient of
determination, respectively
catalyst particles and give the chance to calculate the mass lL
Sc5 Dq = Schmidt number
transfer resistances without caring about the type of catalyst. KS dp
L

The plateau at mass transfer rate against agitation speed plots
is not enough to ensure that the process is limited by either
chemical reaction or external resistances. Conversely, the lim-
iting regime is ensured by the highest resistance. Our method
to determine the limiting regime can be used even if none of
the mass transfer rates can be neglected. To justify the pro-
posed methodology by comparing our results with those in the
literature, we developed correlations of KL  a and KS  aS . The
developed correlations are in agreement with the literature.
Additional work is needed to clarify the effects of pressure on
external mass transfer resistances, especially on liquid-solid
mass transfer resistance.
Acknowledgments
The generous support by Syngenta, EPSRC funding and
the University of Leeds is acknowledged.
Notation
B, B1 = constant terms in Eqs. 22, 25, and 26
b1 = exponent of superficial gas velocity in Eq. 22
CH2 ;i = concentration of hydrogen in gas-liquid interface,
kmol=m3 liquid
CH2 ;L = concentration of hydrogen in liquid phase,
kmol=m3 liquid
CH2 ;S = concentration of hydrogen at catalyst surface,
kmol=m3 liquid
CR2CH5CH2;L = concentration of unsaturated organic compound at
catalyst surface, kmol=m3 liquid
CR2CH5CH2;L = concentration of unsaturated organic compound in
liquid phase, kmol=m3 liquid
CH2M1 = concentration of adsorbed hydrogen at the active
sites of catalyst per area of catalyst, kmol=m2 catalyst
CM1 , = CM2 5 concentration of active sites of catalyst per
area of catalyst, kmol=m2 catalyst
CP = concentration of adsorbed unsaturated organic
compound at the active sites of catalyst
per area of catalyst, kmol=m2 catalyst
Dim ; DR = diameter of impeller and reactor, m
D = diffusion coefficient, m2 =min
dp = diameter of particle, m
H = blade height of impeller, m
HE = Henry constant, Pa  m3 =kmol
KG = gas-liquid mass transfer coefficient related
to gas side film, kmol=Pa  min  m2
KL = gas-liquid mass transfer coefficient related to
liquid side film, m=min
KS = liquid-solid mass transfer coefficient, m=min
KH , = KR 5 chemisorption equilibrium
constants, m3 liquid=kmol compound
0
kobs = observed rate constant for first-order reaction
based on unit catalyst mass, m3 liquid=kg catalyst  min
ko0 = corrected observed rate constant for
first-order reaction based on
2
unit catalyst mass, m3 liquid  kmol H2 0:5 =kg
3 0:5
catalyst  min  m liquid  kmol R2CH5CH2
MTR = mass transfer rate, kmol=m3 liquid  min
N = stirrer speed, rpm
Sh5 D =Sherwood number
T= temperature, K
usg = superficial gas velocity, m/min
VG , = VL 5 volume of gas phase and liquid phase
in the reactor, m3
vL = kinematic viscosity of liquid phase, m2 =s
WC = mass of catalyst, kg
Greek letters
a = gas-liquid surface area, m2 =m3 of liquid
as = area of catalyst per weight of catalyst, m2 =kg catalyst
a1 = exponent of power input per volume of liquid in Eq.
22
b = Vita factor
e = effectiveness factor
 = energy dissipation rate, J  min21 kg21
lL = dynamic viscosity, kg m21 s21
qL , = qp 5 density of liquid phase and solid particle, kg/m3
XH2 tot , XH2 ;i2L , = XH2 ; L2S ; XH2 ; R 5 mass transfer resistances, min
X0H2 ; L2S , = X0H2 ; R 5 mass transfer resistances based on catalyst
concentration, min  kg catalyst=m3 liquid
Subscripts
i= gas-liquid interface
G= gas phase
L= liquid phase
S= solid phase
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Manuscript received Apr. 14, 2016, and revision received Sep. 26, 2016.
January 2017 Vol. 63, No. 1 AIChE Journal