Chemical Engineering Science 54 (1999) 2793}2798

Modelling and scale-up of a loop reactor for hydrogenation processes

Juha Lehtonen , Jyri Kaplin
, Tapio Salmi
*, Heikki Haario, Antti Vuori, Esko Tirronen
Nerte Technology Centre, Box 310, FIN-06101, Porvoo, Finland

Laboratory of Industrial Chemistry, As bo Akademi, FIN-20500 Turku, Finland
Profmath Oy, FIN-00120 Helsinki, Finland
Kemira Agro Oy, Research Centre, FIN-02271 Espoo, Finland

Abstract

A dynamic model for the scale-up of semibatch loop reactors was developed. The mathematical model comprises the essential parts
of the loop reactor: the reaction vessel, the ejector and the circulation loop. Tanks-in-series and axial dispersion concepts were applied
on the description of the non-ideal #ow pattern of the reactor. The dynamic axial dispersion model was discretized with "nite
di!erences with respect to the spatial coordinate, and the created ordinary di!erential equations were solved with the backward
di!erence method suitable for sti! di!erential equations. The loop reactor model was tested with a case study, a homogeneously-
heterogeneously catalyzed reaction system, reductive alkylation of aromatic amines. Simulations showed that rate equations obtained
from laboratory-scale experiments can be successfully combined to the #ow model of the loop reactor: the behaviour of a large-scale
loop reactor was predicted with satisfactory accuracy.  1999 Elsevier Science Ltd. All rights reserved.

Keywords: Loop reactor; Scale-up; Dynamic modelling; Reductive alkylation

1. Introduction ature control of exothermic reactions and for avoiding

Loop reactors represent a very attractive alternative
technology for hydrogenation processes. A typical loop
reactor consists of a vessel, an ejector and a circulation
loop equipped with a pump (Fig. 1). The bene"t of a loop
reactor is e$cient gas}liquid mass transfer which is
accomplished with the ejector. Typically no mechanical
agitation is needed.
Previous investigators (Cramers et al., 1992a, b, 1993,
Dutta and Raghavan, 1987, Dirix and van der Wiele,
1990) have made exhaustive studies of the mass transfer
properties of loop reactors; particularly, the hydrody-
namics of the ejector has been investigated, and correla-
tions for the mass transfer coe$cients and interfacial
areas have been developed (e.g., Dirix and van der Wiele,
1990). Typically, the loop reactor system is operated in
semibatch mode, i.e., one of the reagents is placed in the
vessel, but the other reagents are fed into the #uid phase
during the reaction, which is favourable for the temper-
*Corresponding author. Tel.: 00358 2 2154427; fax: 358 2 215 4479;
e-mail: tapio.salmi@abo.".
undesirable side reactions due to high concentrations
of the reagents. The gas pressure over the #uid phase
is continuously regulated to maintain isobaric
conditions.
In order to achieve the very best performance of a loop
reactor, mathematical modelling is necessary. Principally
many di!erent modelling approaches could be taken,
ranging from simple case-dependent ad hoc models to
a complete modelling of the #ow pattern (computational
#uid dynamics). An appropriate model for the loop reac-
tor should ful"l at least the following requirements: the
reaction kinetics should be described in a realistic } but
not too sophisticated } way, the non-idealities of the #ow
pattern should be included, and, "nally, the dynamic
characteristics of the reactor should be a vital part of the
model.
The present contribution is devoted to the develop-
ment of a realistic model for dynamic loop reactors. The
modelling is based on the classical concepts of tanks-in-
series and axial dispersion; the reactor dynamics is
included and interfacial mass transfer is described
with correlations. The model is tested with a case study:
reductive alkylation of aromatic amines.

0009-2509/99/$ } see front matter  1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 9 8 ) 0 0 5 0 2 - 8
2794 J. Lehtonen et al. /Chemical Engineering Science 54 (1999) 2793}2798

balance equation:
dc
*G"r #r o c #N a
dt G  G   + *G 4

c !c
# *G *G . (3)
q

Indices of loop reactor parts are revealed in Fig. 1, and
the introduced quantities are explained in Notation. The
volume of the liquid phase was updated with <Q (con-

stant volumetric #ow rate). Similarly, the new values for
the catalyst bulk density were calculated from the actual
liquid phase volume. When then tanks-in-series-model
was used, a separate liquid-phase balance was applied for
each mixing unit.
The loop part of the reactor was described alterna-
Fig. 1. Schematic structure of a loop reactor. tively with the tanks-in-series model or with the axial
dispersion model. However, since no gas bubbles were
present in the loop, the interfacial #ux term (N ) was
*G
ignored from Eq. (4). For the axial dispersion model, the
dynamic mass balance for an arbitrary liquid-phase com-
2. Liquid-phase mass balances ponent has the form
dn
The mass balances for the components in the *IG"r <#r m c
liquid phase includes the contributions from dt IG   I IG   I +
catalytic and noncatalytic generation rates, the


dc dc
component #uxes through the gas}liquid interphase ! w *IG#D *IG < . (4)
* dl * dl I
as well as the component #ows. Consequently,
using the tanks-in-series model, the general mass By assuming the constant values for the volumetric #ow
balance of an arbitrary compound in the liquid phase rate and the axial dispersion coe$cient, the "nal form of
can be written as the mass balance equation becomes
dn dc dc dc
*G"r < #r m c #N A *IG"r o c !w *IG#D *IG .
dt G   * G     + *G  dt IG  
#r
IG   I + * dl * dl
#nR #nR  !nR  , (1) (5)
*G *G *G
where m and c denote the mass of the catalyst and the
 +
concentration of the active metal on the catalyst surface,
3. Gas-phase mass balances and correlations
respectively. Assuming that the volume of the liquid
phase is changed exclusively due to the reactant
For the gas phase, it was reasonable to assume that the
feeding (i.e., d< /dt"<Q ), the mass balance can be re-
*  only gas-phase component of importance is hydrogen.
written to
The mass balance equation of hydrogen is given by
dc
*G"r #r o c #N a dn
dt G   G   + * 4 % &"!N A #nR . (6)
dt %&  %&
c !c c !c
# *G *G# *G *G , (2) However, the reactor temperature and the hydrogen
q q
  pressure were constant, which implies that c "con-
&
where o "m /< . Eqs. (1) and (2) are valid for stant and, consequently, dc /dt"0. Thus the gas-phase
 * &
the upper part of the reaction vessel, where the feed of mass balance of hydrogen was not directly utilized in the
the liquid reactant is usually introduced. The modelling. The hydrogen concentration in the gas phase
volumetric ratio of upper and lower parts is an was calculated from the ideal gas law. The partial pres-
adjustable model parameter; usually the ratio 1 : 1 is sure of hydrogen was obtained from the total pressure
chosen (see dashed line in Fig. 1). For the lower part corrected with the vapour pressure of methanol using
of the reaction tank, the reactant feed is ignored and Raoult's law and the vapour pressure correlation of
we obtain analogously with Eq. (2) the following Wagner (Reid et al., 1988). The interfacial #ux of
 J. Lehtonen et al. /Chemical Engineering Science 54 (1999) 2793}2798
hydrogen was calculated from the simple two-"lm model,
N a"k a(c /K !c ), (7)
*& & %& & *&
where k is the overall mass transfer coe$cient:
&
(1/k )"(K /k )#(1/k ). The gas}liquid equilib-
& & *& %&
rium ratio of hydrogen (K ) was estimated from a
&
hydrogen solubility correlation in methanol (Fogg and
Gerrard, 1991).
Since bubble #ow prevailed in the reactor, the correla-
tion of Dirix and van der Wiele (1990) was used for the
gas}liquid mass transfer coe$cient in the reactor vessel
and in the ejector:
G D
k a"a Re . (8)
* L G#¸ <
CH
The di!usion coe$cient of hydrogen was estimated from
the well-known equation of Wilke and Chang for di!u-
sion in liquid mixtures (Reid et al., 1988). The following
numerical values were used: < "14.3 cm/mol,
"1.9 some extent hydrogenated to the corresponding primary
&
(methanol) and
"1.0 (aromatics). The viscosity of the alcohol.
liquid phase was calculated as a mixture viscosity of
methanol and aromatic reagent using the equation of
Teja and Rice (Reid el al., 1988).
4. Numerical solution strategies
The model based on tanks-in-series concept forms
a system of ordinary di!erential equations (ODES), an
initial value problem, which was solved with the back-
ward di!erence method implemented in the software
ODESSA (Hindmarsh, 1983).
The dynamic axial dispersion model results in a system
of parabolic partial di!erential equations (PDEs). The
PDEs were converted to ODEs by discretizing the spatial
coordinate with "nite di!erences. The "rst derivatives
originating from the plug #ow term (w (dc /dl)) were
* *G
approximated with backward di!erences, whereas the
second derivatives originated from axial dispersion
(D (dc /dl)) were discretized with central di!erences.
* *G
The software of Schiesser was used in the discretization
(Schiesser, 1991). The initial value problem (ODEs)
created in this way was then solved numerically with
the backward di!erence method. The models were
implemented in a simulation and parameter estimation
software MODEST (Haario, 1994).
2795
5. Case study: reductive alkylation
Reductive alkylation of aromatic amines is applied e.g.,
in the production of intermediates for dye-stu! industry.
A primary amine reacts in liquid phase with an aldehyde,
and water is abstracted yielding an imine. The double
bond of the imine is then hydrogenated further giving
a secondary amine. The monoalkylated secondary amine
can follow an analogous reaction path, giving a dia-
lkylated tertiary amine as the "nal reaction product. The
reaction sequence is summarized below.
Besides these main reactions, several side reactions can
take place such as dimerization and alkylation of the
aromatic ring. A complete reaction scheme has been
designed by our group (Lehtonen et al., 1998).
The hydrogenation of the imine is a heterogeneously
catalyzed process that is carried out over a noble metal
catalyst (Pt or Pd). This implies that the aldehyde is to
To obtain the rate parameters, kinetic experiments
were performed in a laboratory-scale semibatch auto-
clave (2000 ml) with "nely dispersed Pt catalyst. The
hydrogen pressure was 15 bar and the temperature was
varied within the range of 30}753C. The amount of cata-
lyst was typically 1}3 g/mol aromatic amine in the
experiments. Samples were withdrawn from the liquid
phase and analysed with high performance liquid
chromatography.
Examples of typical kinetic curves obtained with an
aromatic reagent having an alkyl substituent in the
ortho position are depicted in Fig. 2. The ring alkylation
was omitted from the quantitative kinetic modelling,
because its role turned out to be negligible (Lehtonen
et al., 1998).
Rate equations for the mono- and dialkylation
processes were derived according to the following
principles: the primary reaction of the aldehyde (I)
(non-catalytic step) and the hydrogenation step of
the imine (III) (catalytic step) were presumed to be
rate determining, while the water abstraction step (II)
as well as the adsorption and desorption steps were
assumed to be rapid (see the reaction scheme). Based
on these hypotheses, the rate equation for the imine
generation and hydrogenation were obtained. For the
sake of illustration, the rates of steps I and III in the
2796 J. Lehtonen et al. /Chemical Engineering Science 54 (1999) 2793}2798

to be able to compare the tanks-in-series and axial

dispersion models, the following equation was used to
relate the number of tanks ( j ) and the Peclet number (Pe)
(Salmi and Lindfors, 1986).

Pe
j" . (13)
2(Pe!1#e\.C)

The relation is based on equal variances of the models.

Fig. 2. An example of a "t of the kinetic model.
reaction scheme are listed below:
Some simulation results are displayed in Fig. 3. It can be
concluded that the reactor performance varies with vary-
ing Peclet number in the loop. The e!ect of Peclet num-
ber is somewhat opposite to the steady-state behaviour:
in the semibatch loop reactor, the reactions are
enhanced with decreasing Peclet number.
The rate equations developed for reductive alkylation
(see section case study), including the values of the kinetic
parameters, were implemented in the loop reactor model
and "nally the loop reactor model was veri"ed with an


c c
R "k c c ! ' &- (9) independent simulation, which was compared with plant
' '  0Y!&- KK
' '' data. The progress of a large-scale alkylation process is
k c c shown in Fig. 4. A comparison with experimental data
R " ''' ' & . (10)
''' (1#K c #(K c # K c ) reveals that the model can very satisfactorily predict the
' ' & & H H comportment of the large scale process and thus it can be
The rate equations for dialkylation are exactly analogous used for scale-up purposes.
with Eqs. (9) and (10). Parameter a in the hydrogen mass transfer correlation
For the catalytic hydrogenation of the aldehyde, the equation (Eq. (8)) applied to our loop system using
following rate equation was used: kinetic parameters obtained from the laboratory scale
experiments and estimated as 1.5;10\. Number of
k c c
R " -& 0Y!&- & . (11) tanks in the reaction vessel was "xed to 2 and in the loop
-& (1#K c #(K c # K c )
0Y!&- 0Y!&- & & H H to 5 (Pe"8.87). For the reaction vessel, two tanks were
The generation rates of the components were obtained concluded to be a suitable number, since the vessel was
from the stoichiometric relations, rather well backmixed. As can be seen from Fig. 3, "ve
tanks for the loop was enough to describe a behaviour
r " r #( r )o c , (12) close to plug #ow. The reaction system was simulated at
G H   H  +
where the indices noncat and cat refer to the homogene-
ous reactions and heterogeneous catalytic reactions,
respectively.
The semibatch reactor model was solved with the
backward di!erence method during the estimation of
the parameters. The parameter estimation was carried
out with a hybrid simplex-Levenberg}Marquardt algo-
rithm by minimizing the weighted sum of residual
squares (Haario, 1994). The parameter estimation results
were presented in the previous paper (Lehtonen et al.,
1998) of our group, but an example of the model "t is
displayed in Fig. 2. As the "gure reveals, the model is able
to predict the kinetic behaviour of the system and it is
thus su$ciently sophisticated to be used in loop reactor
simulations.

6. Simulation results

The loop reactor models were simulated using the Fig. 3. Loop reactor simulation with di!erent Peclet numbers in the
degree of backmixing as one of the parameters. In order loop.
 J. Lehtonen et al. /Chemical Engineering Science 54 (1999) 2793}2798 2797

Fig. 4. Veri"cation of the kinetic model in a large scale loop reactor.

313 K. The simulated concentration pro"les are dis-

played in Fig. 5. The "gures indicate that the concentra-
tion pro"les inside the reactor are quite #at, except for
hydrogen. This is explained by the rather slow reaction
rate compared to the circulation velocity.
Finally under the same conditions, the reaction tem-
perature was varied between 288}348 K. The concentra-
tions of the monoalkylated product (B) is depicted in
Fig. 6. Fig. 6. Simulation of reductive alkylation i a loop reactor with temper-
The simulations reveal that there exists an optimal atures 288.15}348.15 K, step 8.57 K.
reaction time and temperature for the maximization of
the monoalkylated product: at low temperatures, the
reaction time becomes very long, and at high temper-
atures, the monoalkylated product reacts rapidly to the c concentration, mol/m
dialkylated product. D axial dispersion coe$cient, m/min
G volumetric gas #ow in the ejector, m/min
j number of tanks
Notation k mass transfer coe$cient, m/min
k rate constant
a speci"c mass transfer area, m/m k overall mass transfer coe$cient, m/min
A mass transfer area, m K adsorption equilibrium coe$cient

Fig. 5. Simulation of three-dimensional concentration pro"les.

2798 J. Lehtonen et al. /Chemical Engineering Science 54 (1999) 2793}2798

K gas}liquid equilibrium ratio  loop

l length, m  ejector
¸ volumetric liquid #ow in the ejector, m/min
m mass, kg Abbreviations
n amount of substance, mol
n molar #ow, mol/min A primary amine (Ar}NH )

N #ux, mol/m min B monoalkylated secondary amine
p pressure, bar (Ar}NH}CH R)

Pe Peclet number C dialkylated tertiary amine (Ar}N}(CH R) )
 
r generation rate Ar aromatic ring
R reaction rate
Re Reynolds number
t time, min References
< volume, m
< molar volume (m/mol) in Wilke}Chang equa- Cramers, P.H.M.R., van Dierendonck, L.L., & Beenackers, A.A.C.M.
tion (1992a). In#uence of the gas density on the gas entrainment rate
<Q volumetric #ow, m/min and gas hold-up in loop-venturi reactors. Chem. Engng Sci., 47,
2251}2256.
w velocity, m/s Cramers, P.H.M.R., Beenackers, A.A.C.M., & van Dierendonck, L.L.
(1992b). Hydrodynamics and mass transfer characteristics of
Greek letters a loop-venturi reactor with a down#ow liquid jet ejector. Chem.
Engng Sci., 47, 3557}3564.
Cramers, P.H.M.R., Smit, L., Leuteritz, G.M., van Dierendonck, L.L.
a coe$cient (Eq. (9)) & Beenackers, A.A.C.M. (1993). Hydrodynamics and local mass
o catalyst bulk density, kg/m transfer characteristics of gas-liquid ejectors. Chem. Engng J., 53,
q space time (q "< /<Q , q "< /<Q ) 67}73.
 *   *  

association factor in Wilke}Chang equation Dirix, C.A.M.C., & van der Wiele, K. (1990). Mass transfer in jet loop
reactors. Chem. Engng Sci., 45, 2333}2340.
Dutta, N.N., & Raghavan, K.V. (1987). Mass transfer and hydro-
Superscripts and subscripts dynamic characteristics of loop reactors with down#ow liquid jet
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(p. 300}300). Chichester: Wiley.
circ circulation Haario, H. (1994). MODES¹-;ser1s Guide, Profmath Oy, Helsinki.
ej ejector Hindmarsh, A.C. (1983). A systematized collection of ODE-solvers.
i component index In R. Stepleman et al. (Eds.). Scienti,c computing, (pp. 55}64).
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principles of modelling of homogeneous-heterogeneous reactions in
¸ liquid phase the production of "ne chemicals. A case study: reductive alkylation
M active metal of aromatic amines. Org. Proc. Res. Dev., 2, 78}85.
n nozzle Reid, R.C., Prausnitz, J.M., & Poling, B.E. (1988). ¹he properties of
noncat non-catalytic gases and liquids (4th Ed.), Singapore: McGraw-Hill.
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