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Article history: A model was developed to simulate tubular enzymatic membrane reactors under three different
Received 11 June 2014 congurations: dead-end, tangential ow with a porous enzymatic membrane and a non-permeable
Received in revised form enzymatic wall. The simulations were applied to analyze the inuence of reactor conguration, kinetics
25 August 2014
and mass transport conditions over the reactor performance in order to identify the main aspects to be
Accepted 10 September 2014
Available online 19 September 2014
taken into consideration for attaining optimal designs. The non-permeable enzymatic wall conguration
under the evaluated conditions seems to be more valuable than the dead-end case in terms of substrate
Keywords: conversion and the tangential conguration looked more favorable to promote the best conversion in the
Enzymatic membrane reactor permeate but not in the retentate. It was demonstrated that for a similar value, the Damkhler number
Modeling
can result in very dissimilar performances. The simulated results demonstrated that the most signicant
Simulation
variable of the global performance of the enzymatic membrane reactors is the reaction kinetics: fast
Sensitivity analysis
reactions attained very considerable conversion values under very different conditions.
& 2014 Elsevier B.V. All rights reserved.
1. Introduction and are compiled in bibliography [7], but in a broad framework, all
different immobilization strategies can be categorized in one of
Enzymes are gaining relevance as biocatalysts in industrial the following groups: adsorption, covalent linking, entrapment
processes, as their capacities have been adapted during the last encapsulation, cross-linking or afnity [8]. Membranes are con-
50 years for successful production of some commodities, ne sidered as very attractive supports for immobilizing enzymes since
chemicals and pharmaceuticals in an environmentally friendly they can be placed in multifunctional membrane reactors, which
way (high reaction rates at room temperature and pressure with- integrate biocatalytic reaction, product separation and enzyme
out auxiliary chemicals). Enzymes are specically useful to facil- recovery [911]. Enzymatic membrane reactors (EMRs) can over-
itate the synthesis and modication of organic molecules by come some of the negative aspects that are related to immobiliza-
chemo-, regio-, and stereoselective bond-forming and -breaking tion and show some advantages over other alternatives, but some
reactions [1,2]. But enzymes have to compete economically with disadvantages are still apparent as summarized in Table 1 [10].
inexpensive traditional chemical processes which are nowadays EMRs contribute to the implementation of continuous operation
industrially established. Therefore, the recovery and reuse of mode and avoid the intrinsic discontinuous nature of batch processes
enzymes, which are generally expensive, becomes really essential and their problems. Nevertheless, although several continuous
in most cases in order to assure the economic viability of the enzymatic processes have been fully developed, improvement of
processes [3,4]. Indeed, immobilization of enzymes is generally the entire processes is still required to maximize the benets derived
required in industry. from their use [912]. Reaction engineering must provide solutions
In addition, immobilization can also improve enzyme perfor- to improve enzymatic processes at the commercial level [13].
mance by increasing their activity, stability and selectivity and Decisions made in reactor design have a very signicant impact on
allowing optimal process reaction conditions, such as acidity, the enzymatic process performance, but there are no simple and
alkalinity, organic solvents or elevated temperatures [5,6]. Many direct procedures available to determine the optimal conditions [14].
immobilization methods and protocols have been put into practice These reaction conditions also determine the downstream processing
and, under the consideration of the high importance of the costs due
n
to downstreaming, have a deep impact in the economic viability of
Corresponding author. Tel.: 33 467149149; fax: 33 467149119.
E-mail address: Jose.Sanchez-Marcano@univ-montp2.fr (J. Sanchez-Marcano).
the whole process [15].
http://dx.doi.org/10.1016/j.memsci.2014.09.020
0376-7388/& 2014 Elsevier B.V. All rights reserved.
190 R. Abejn et al. / Journal of Membrane Science 473 (2015) 189200
Table 1 which are more usual at industrial scale like the tangential cong-
Advantages and drawbacks of EMRs. Adapted from [10]. uration. Moreover, a detailed theoretical analysis was carried out in
order to study the main process variables controlling the global
Advantages Drawbacks
performance and conversion of EMRs. For this purpose we based
Effective retention and reuse of catalyst Enzyme activity decay our simulations on the different enzymatic kinetics reported in the
Heterogeneous reaction literature. This analysis was carried out considering initially
Continuous mode operation
conditions the Damkhler number, and then carrying out a careful analysis
Reduction in substrate/product inhibition Polarization layers
of the inuence of the different parameters on the conversion of
Final product free of enzyme Membrane fouling
Possible less enzyme activity enzymatic membrane reactors in tangential conguration.
Enhanced enzyme stability when grafted
when grafted
Decrease of diffusional limitations
Process intensication (single-step reaction
and separation) 2. Process modeling and case study resolution
Fig. 1. Reactor congurations: (a) Enzymatic non-permeable wall, (b) Tangential and (c) Dead end.
1) radial and axial uxes in the inner side of the tubular mem-
branes and in laminar conditions;
2) reaction takes place only at the surface of the separative layer;
Table 2 3) radial ux occurs through the separative layer and then
Membrane layer characteristics [29]. through the membrane porosity;
4) the permeate ux is immediately depleted out of the reactor.
Filtration active gel layer Support
Thickness (m) 1.4 10 5 1.5 10 3 The experimental Lp reported in Table 2 allowed to calculate
Porous diameter (m) 8 10 7 1 10 5 the derived membrane permeability coefcients by using the
Porosity ( ) 0.37 0.37 HagenPoiseuille equation:
Tortuosity ( ) 1.0 1.0
Hydraulic permeability JP
3.2 10 10 5.6 10 7 LP 2
(m s 1 Pa 1) P
Material permeability (m2) 4.48 10 18
8.34 10 13
dP
2
LP U 3
32 U U
LP U U 4
a thin ltration layer of 8.0 10 7 m of mean pore size supported
on a thick porous ceramic support with a mean pore size of where JP is the permeate ux, P is the transmembrane pressure,
1.0 10 6 m. A very thin (less than one micron of thickness) is the porosity, is the tortuosity, dP is the pore diameter, is the
but continuous gelatin layer was deposited on the internal surface membrane thickness, and m is the dynamic viscosity.
of the ceramic membranes, the enzymes were immobilized on The liquid velocities in channels were calculated from station-
the surface of this very thin cross-linked gelatin layer. The applied ary incompressible NavierStokes equations for a laminar regime
immobilization protocol, was originally developed by this as follows:
research group for the immobilization of -chymotrypsin [30] U u Uu P U u U g 5
but successfully adapted to other enzymes like CALB [31] and
laccase [32,33]. In our preliminary work [29], we considered Uu 0 6
that the structural characteristics of the support were not where is the uid density, u is the velocity and P is the pressure.
affected by the gelatin deposition and that enzymes were largely In the porous matrix (ceramic and gel layers of the membrane)
located on the membrane surface. In this work we took the same Brinkman equations describe in an adequate way the mass
assumption. transfer [34,35]:
To simplify the geometry, thickness and pore diameter of each
1 2U
layer were considered constant and equal to the average values Uu P U2 u U U u U g 7
shown in Table 2, which includes also the hydraulic permeability 3
coefcients LP. The permeability coefcients were obtained from
Uu 0 8
experimental permeate uxes because the cross-linked gelatin
192 R. Abejn et al. / Journal of Membrane Science 473 (2015) 189200
The concentration eld C for each specie was calculated from 2.3. Models resolution
the mass balance and reaction rate taking into account the
reactant (butyl acetate) consumption ( vR) or product (acetic The explained mathematical model was implemented in COM-
acid) appearance (vR). As far as the reaction extend was based on SOL Multiphysics 4.4, by coupling free (Eqs. (5) and (6)) and
the reactant consumption for the modeling, the following equation porous media (Eqs. (7) and (8)) ows, transport of diluted species
can be employed: (Eq. (9)), and reaction kinetics (Eq. (12)) considering that the
enzymatic reaction takes place at the inner surface of retentate
u U C DX U 2 C vR 9 channel. The resolution was carried out for steady state conditions.
The mono-channel simulated membrane reactors can be repre-
where DX is the diffusion coefcient. On the contrary of some
sented by an axisymmetric 2D scheme, the enzymes were con-
previous literature works, the diffusion coefcients in the liquid
sidered to be grafted on the internal surface of the membrane.
media were not considered identical but they were estimated
In order to optimize the calculation time, the simulations were
independently for each compound with the Wilke and Chang
done taking into account this symmetry and the results were given
correlation [36]: as the evolution of concentrations inside the tubular membrane
but representing only the 2D prole of the inner compartment and
M W 0:5 T
DX 7:4 U10 13 10 the membrane (retentate, gelatin thin layer and porous support)
V 0:6
M following the schematic draw shown in Fig. 2. The membrane
supports are 1.3 10 1 m long (L) and their internal and external
where is the association factor (2.6 for water), MW is the
molecular weight of solvent (water in this example), T is the
temperature, is the viscosity, and VM is the molecular volume of
each specie, this last parameters was calculated for each compo-
nent according to Prausnitz et al. [37]. The values of diffusion
coefcients calculated are presented in Table 3. Inside the pores of
the membrane layers, the diffusion coefcient values were cor-
rected with the porosity and tortuosity values (0.37 and 1 for the
proposed case, see for instance Table 2):
DXP DX 11
where DXP is the corrected diffusion coefcient. For further details
about the mathematical model, specically about the mass and
momentum balances related to Brinkman equations, bibliography
can be consulted [38].
Previously obtained experimental results about butyl acetate
hydrolysis were successfully tted to the MichaelisMenten kinetics
reaction model:
CS
vMM vMAX 12
CS K M
N Xin N Xout 7 N XR 13
Table 3
Diffusion coefcient values.
Table 4
Initial and boundary conditions.
The model had been validated in a previous work for the dead-
end conguration [29]. The experimentally obtained results were Fig. 4. Radial ow velocity (m/s) prole for the different reactor congurations:
(left) Enzymatic non permeable wall; (center) Tangential conguration; and (right)
compared to the simulated ones and, as the found differences
Dead-end conguration.
were not signicant, the model was concluded as valid. Therefore,
the same modeling approach was followed for the other two
congurations investigated in this work (enzymatic wall and axial velocity and only at the end of the inner channel the radial
tangential ltration conguration). In all simulation gures shown component dominates over the axial one.
below, the enzymatic layer and membrane support are placed at The tangential mode can be analyzed as an intermediate
the right side of the illustrations as shown in the schematic situation between the two extreme cases. The feed ow of the
representation in Fig. 2. tangential mode is the sum of the one of the other two cases and,
The hydrodynamics proles, expressed as axial and radial ow consequently, the corresponding ows of permeate and retentate
velocities, are shown in Figs. 3 and 4 respectively. The ow streams are similar to the resulted ones in the extreme cases.
limitations that are imposed under enzymatic wall (no permeate The ow prole inside the membrane is analogous to that
stream) and dead-end (no retentate stream) congurations have obtained for the dead-end conguration whereas the ow prole
clear impact over the hydrodynamics. The enzymatic wall mode is in the inner channel looks like the enzymatic wall case. Never-
characterized by null radial velocity as uid is not allowed to theless, some differences are visible. The axial velocity prole
permeate through the support, so a totally developed laminar shows how the higher feed ow implies higher initial velocity.
ow along the axial direction can be observed. By contrast, the However, the velocity is reduced along the reactor length as a
dead-end mode does not allow retentate outlet and all the feed consequence of the mass transfer by permeation. Otherwise, the
stream has to permeate. As a consequence, the axial velocity radial velocity prole differs only in the boundary effect on the
becomes negligible near the end of the inner channel whereas inner channel outlet when compared to the dead-end case.
the radial velocity is almost constant along the membrane length The concentration proles of the substrate A (butyl acetate) are
(except for the both ends where some boundary effects appear). shown in Figs. 5 and 6. To have a better understanding of the
Nonetheless, the radial velocity magnitude is lower than the results, three different conversion expressions are dened: global
194 R. Abejn et al. / Journal of Membrane Science 473 (2015) 189200
Fig. 6. Detail of the substrate (A) concentration (mol m 3) prole for the outlet of
the enzymatic non-permeable wall conguration.
Fig. 5. Substrate (A) concentration (mol/m3) prole for the different reactor
congurations: (left) Enzymatic non-permeable wall; (center) Tangential cong-
uration; and (right) Dead-end conguration.
F 0 U C 0 F perm U C perm F ret U C ret
X global 100 14 the substrate is attained close to the wall, with a minimal
F 0 U C 0 concentration of 21.4 mol m 3.
C 0 C ret The global conversion in the tangential conguration is 3.5%,
X ret 100 15
C0 but it has to be kept in mind that the treated ow is just the
double of the feed ow of the dead-end conguration. The
C 0 C perm conversion for the permeate stream is 6.9%, very close to the value
X perm 100 16 obtained for the dead-end case. However, the conversion for the
C0
retentate stream is very low, only 0.1%. Indeed, the major part of
Global conversions were obtained by integrating the concen- the uid that gets in contact with the enzymatic layer placed at
tration proles and ows through the different reactors volumes. the membrane internal surface, crosses the membrane as soon as
The enzymatic wall conguration is slightly more effective than it had reacted and leaves the system as permeate, not as retentate,
the dead-end one (global conversions of 7.2% and 7.0% are reached so that the uid has not as much contact time as in the case of the
respectively). In the enzymatic wall reactor, a high conversion of non-permeable enzyme support.
R. Abejn et al. / Journal of Membrane Science 473 (2015) 189200 195
Fig. 8. Inuence of the transport rate in terms of axial and radial Damkhler number over the conversion of butyl acetate in EMR in a non-permeable enzymatic wall
conguration (a) and dead-end conguration (b).
In order to analyze more in detail for the tangential congura- axial and radial Damkhler numbers:
tion the inuence of the relative ows of retentate and permeate,
Reaction rate v UC S =C S K M
we carried out simulations considering different ratios of perme- DaZ MAX 17
Axial mass rate Q RET UC S =ARET
ate/retentate (Qperm/Qret) and calculated the hydrolysis conver-
sions reached in each compartment. As it was explained Reaction rate vMAX UC S =C S K M
previously for these simulations, global conversions and ows DaR 18
Radial mass rate Q PERM UC S =APERM
were integrated through the different volumes of the reactors.
The results presented in Fig. 7 show that at very low Qperm/Qret where QRET and QPERM are the ows of the retentate and permeate
ratio the axial and global conversion are very low, in such case the streams respectively, and ARET and APERM are the outlet areas of the
axial ow rate is very high and the contact time is very short, retentate and permeate streams, which correspond to the surfaces
whereas the permeate ow rate is low and then even if its perpendicular to the ow direction, i.e. the cross section of the
conversion is not negligible it has a very low inuence on the inner channel for ARET and the external surface of the membrane
global conversion because its contribution to the total volume is support for APERM.
very small. On the contrary, at very low Qperm/Qret ratio we For the simulations we calculated DaZ and DaR and conversions
approach the conditions and conversion of the dead-end cong- considering the actual measured kinetics of butyl acetate hydrolysis
uration. Indeed, the conversion of the permeate ow is always (Eq. (12), where vMAX 1.572 10 4 mol s 1 m 2 and KM
higher than the retentate ow because all the permeate has been 20.19 mol m 3 [29]) and varying theoretically the ow rates (axial
in contact with the biocatalyst, whereas only a small fraction of and radial) from 3.2 10 3 m s 1 to 3.2 10 7 m s 1. The simulation
the retentate (near the enzymatic membrane) is really in contact results are shown in Fig. 8.
with the grafted enzymes. These results are in good agreement The obtained results show the same trend: high Da numbers
with the concept of ow-through membrane reactor which are required to achieve high conversion. These high Da numbers
considers that the physical approaching of substrates and catalyst represent situations with small feed ows, and then high resi-
or biocatalyst by the permeation is fundamental for the effective- dence time, which afford these membrane reactors to attain even
ness of the membrane reactors. complete conversion. If we consider the actual experimental
After the analysis of these initial simulated results for the conditions for the dead-end conguration with an experimental
hydrolysis of butyl acetate, two ideas can be outlined. On the one ow rate of 3.2 10 2 m s 1 it corresponds to a Da of 7.2 10 2,
hand, the enzymatic wall conguration under these particular and a conversion of 7%. This result indicates that in the actual
conditions seems to be more advantageous than the dead-end experimental conditions [29], the process is controlled by the
case in terms of substrate conversion, but under this situation kinetics (very low Da).
ltration is not carried out. On the other hand, in terms of The sigmoidal shape of the obtained graphs has some clear
global conversion for porous membranes, both tangential and implications in the sensitivity of the reactors: changes in the
dead-end congurations can reach similar results but tangential values that represent extreme conditions (both low and high Da
conguration allows a continuous ltration while giving the numbers values) are much less signicant than the ones in the
possibility of avoiding the formation gel layers and a continuous intermediate range, and therefore, very small improvement of the
permeate ow. conversion can be attained even by important ow modications
The Da number has been frequently used to evaluate and study in these extreme situations.
the sensitivity of enzymatic or other types of reactors performance Nonetheless, the investigated reactors are mainly in the regime
by investigation of the effect of variation of Da number [39,40]. of reaction-controlled process and only under extreme conditions
Thus, the analysis carried out above can also be made considering out of the proposed framework the mass transfer becomes the
the Damkhler number (Da) which is a classical dimensionless controlling agent of the process [41]. The DaZ of the non-
number used to relate the chemical reaction rate to the transport permeable enzymatic wall reactor is lower than 1 for all the
phenomena rate occurring in a reactor. In the case of membrane proposed feed ow range, and, for the case of the dead-end
reactors, the Da has also been studied to determine if the process conguration, none of the values of the DaR is higher than 10.
is controlled by the biological or chemical kinetics or by the mass
transport through the membrane [9]. For this purpose we con- 3.2. A general analysis of the inuence of kinetics and mass transport
sidered only two congurations: the non-permeable enzymatic conditions in EMRs
wall and dead-end. Both congurations present two different
uxes: radial and axial which can be described by two different In order to generalize the model, we will present in the next
Da numbers. The following expressions have been dened for the sections simulations considering different kinetics and mass
196 R. Abejn et al. / Journal of Membrane Science 473 (2015) 189200
Fig. 9. Simulations of an enzymatic non-permeable wall reactor. Inuence of the reaction kinetics and transport terms over: (a) the axial Damkhler number and (b) the
performance expressed as conversion.
transport properties to extend the model to all types of EMRs with DaZ value (0.096). However, as this dimensionless number is the
enzymes grafted at the membrane surface. quotient between the reaction and mass transfer rates, all the
The analyses with different kinetics showed that the results situations that maintain the ratio between both terms do not change
obtained by modifying the reaction rate or the mass transfer the resulting value of the DaZ number, but the operation conditions
conditions led to different results in spite of an identical subse- can correspond to high reaction rate high mass transfer or low
quent Da number. As illustrative example, Fig. 9 compares the reaction rate low mass transfer situations, which entail very
inuence of the reaction and mass terms over the axial Da number different reactor performances.
and the conversion obtained in an enzymatic wall reactor. As it can In Fig. 10 we can notice that the lower substrate concentrations
be observed, diagonal lines in Fig. 9a represent different operation are reached in the case of low reaction rate and low mass transfer.
conditions with identical Da number values, but this pattern is Nevertheless, it is clear that the mass transfer has greater impor-
very dissimilar in Fig. 9b and very different reactor performance is tance than kinetics for the investigated situations. For the case of
expected for points with the same DaZ value. For instance, Fig. 10 equal DaZ number values in enzymatic non-permeable wall
shows the substrate concentration prole of three different situations reactor, the lower the treated ow, the more effective the reaction
in an enzymatic non-permeable wall reactor characterized by a same is (never mind the reduction in the kinetics term). High feed ows
R. Abejn et al. / Journal of Membrane Science 473 (2015) 189200 197
Fig. 11. Inuence of the apparent maximum reaction rate over the performance of
the EMR on tangential conguration expressed as permeate, retentate and global
conversions for a xed apparent MichaelisMenten constant value (KM 20 mol/m3).
The respective feed and permeate ow rates are 18 10 8 and 9 10 8 m3/s.
Fig. 12. Inuence of the membrane permeability over the performance of the
tangential mode reactor expressed as permeate, retentate and global conversions for
intermediate reaction kinetics (vMAX 1.57 10 4 mol/s m2 and KM 20.2 mol/m3).
4. Conclusions
be highlighted from the study of the different congurations. CS substrate concentration (mol m 3)
On the one hand, the non-permeable enzymatic wall conguration C0 feed concentration (mol m 3)
seems to be more advantageous than the dead-end case in terms DaR radial Damkhler number
of substrate conversion for the studied conditions. On the other DaZ axial Damkhler number
hand, the tangential conguration looks more favorable to pro- dP pore diameter (m)
mote best conversions in permeate streams when compared with DX diffusion coefcient (m2 s 1)
retentate streams. DXP corrected diffusion coefcient in pores (m2 s 1)
Kinetics and mass transport parameters were incorporated in Fperm permeate ow (m3 s 1)
Damkhler dimensionless numbers to investigate their inuence Fret retentate ow (m3 s 1)
over the performance of EMRs. Nevertheless, in spite the interest F0 feed ow (m3 s 1)
of Damkhler numbers to determine the controlling step of the JP permeate ux (m s 1)
process in some situations, similar Damkhler values result in very Km MichaelisMenten constant (mol m 3)
dissimilar performances of the EMRs. LP hydraulic permeability coefcient (m s 1 Pa 1)
A detailed analysis of the relative inuence of mass transport MW molecular weight of water (kg mol 1)
and enzymatic kinetics showed that this last process controls NXin inside ux (mol s 1 m 2)
generally the global process. Almost total conversion in the NXout outer ux (mol s 1 m 2)
permeate stream can be attained for the fastest reactions, while NXR reaction ux (mol s 1 m 2)
slow reactions suffer from irrelevant conversions. Nevertheless, P pressure (Pa)
even for very fast reaction rates, the conversion in the retentate T temperature (K)
stream is not signicant, with conversion values not higher than u velocity (m s 1)
1%. The membrane permeability is an important factor to dene VM molecular volume (m3 mol 1)
different types of reactors depending if the outlet stream is VMAX maximal reaction rate (mol s 1 m 2)
preferred as retentate stream (low membrane permeability) or VMM modeled reaction rate (mol s 1 m 2)
permeate stream (high membrane permeability). High feed ows VR reaction rate (mol s 1 m 3)
imply an irrelevant performance and conversion decreases drasti- association factor
cally. Despite of the slower reaction rate consequence of lower membrane thickness
substrate concentration, the obtained results demonstrate how P applied pressure (Pa)
the maximum conversion corresponds to the minimum feed porosity
concentration. material permeability (m2)
Therefore, the concurrence of fast reaction kinetics and high m viscosity (Pa s)
permeability appears as a very promising target because of its great tortuosity
potential to obtain very high conversion for the permeated stream,
so it is clear that the efforts should be oriented to progress in the
achievement of more efcient reaction kinetics. These enzymatic
kinetics improvements can be attained by different ways, including
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