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Chemical Engineering Science 66 (2011) 2285–2297

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Chemical Engineering Science


journal homepage: www.elsevier.com/locate/ces

Attainable regions of reactive distillation—Part III. Complex reaction scheme:


Van de Vusse reaction
Vinay Amte, Sriharsha Nistala, Ranjan Malik, Sanjay Mahajani n
Department of Chemical Engineering, Indian Institute of Technology, Bombay, Powai, Mumbai 400 076, India

a r t i c l e i n f o abstract

Article history: The main underlying principle behind the application of reactive distillation (RD) for selectivity
Received 13 October 2010 enhancement is to facilitate the separation of selected components and favorably manipulate the
Received in revised form composition profiles in the reactive zone to expedite the desired reaction. In this paper, a geometric
3 February 2011
approach of attainable region (AR), which is already developed for conventional reactor network, is
Accepted 6 February 2011
Available online 2 March 2011
extended further to include few representative RD configurations. We define new RD building blocks
and the corresponding composition vectors that indicate a need of networking of RD units among
Keywords: themselves and with conventional reactors to enlarge the set of attainable compositions. A model
Attainable region k1 k2 k3
Chemical reactors reaction scheme of van de Vusse type ðA!B!C, 2A!D) is studied as an illustrative example
Network and an algorithm is developed to obtain the attainable region for the given kinetics, feed composition
Reactive distillation and relative volatilities. In almost all the different cases, which are studied by varying the kinetics and
Selectivity volatility pattern, network consisting of RD units performs better than the conventional reactor
Van de Vusse reaction network.
& 2011 Elsevier Ltd. All rights reserved.

1. Introduction product. The choice of a suitable RD configuration is based on a


parameter called selectivity factor, which is defined as the rate of
Reactive distillation (RD) is by now a well established opera- desired reaction to the rate of undesired reaction (Agarwal et al.,
tion that combines reaction and distillation in a single unit to 2008a). Considering the volatilities of the components and the
offer enhancement in the overall performance of the process. expression of the selectivity factor we can decide whether to conduct
Various commercially important RD processes have already been the reaction in the rectifying section or in the stripping section of a
reported in various reviews in this area (e.g., Sharma and RD column. However, in the case of few complex reaction schemes
Mahajani, 2003; Hiwale et al., 2004; Taylor and Krishna, 2000; selectivity factor alone cannot form a basis for this analysis. The
Malone and Doherty, 2000). The main motivations behind the complexity may arise through the reaction kinetics or through
applications of reactive distillation are enhancement in conver- the vapor–liquid equilibrium. There is no systematic method avail-
sion for reversible reactions and selectivity improvement in the able to obtain the attainable region in such case. In this work, we
case of multiple reaction schemes. While there has been sub- present a synthesis method for obtaining attainable selectivities
stantial experimental and theoretical work reported on equili- with the help of reactive distillation for complex reaction schemes
brium limited reactions, selectivity engineering has not received involving both series and parallel reactions. While the analysis
much attention. The basic principle behind the application of RD presented here is applicable to non-azeotropic systems, it can be
for selectivity engineering is that one can favorably manipulate extended to azeotropic systems with appropriate modifications.
the composition profiles with the aid of distillation attributes to Attainable region (AR) approach which addresses the reactor
expedite the desired reaction. Some of the notable efforts reported in network feasibility was first introduced by Horn (1964). Horn
recent past are for dimerization of isobutene (Talwalkar et al., 2007) pointed out without elaborating on AR boundary that the feasible
and aldol condensation of acetone (Thotla et al., 2007). The reaction region would not necessarily include all stoichiometrically possi-
schemes in both of these cases are relatively simple in the sense that ble compositions as it would be restricted to sets of compositions
they involve only one side reaction in which the desired product that can be realized in all possible reactor systems and mixing.
undergoes further consecutive reaction to yield the undesired Shinnar and Feng (1985) were the pioneers in investigating
thermodynamic constraints on chemical reaction trajectories.
They also used geometric approach to define an attainable region
n
Corresponding author. Tel.: þ91 22 2576 7246; fax: þ 91 22 2572 6895. in a concentration space subjected to the constraints that the free
E-mail address: sanjaym@iitb.ac.in (S. Mahajani). energy for each of the kinetically independent reactions must be

0009-2509/$ - see front matter & 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2011.02.008
2286 V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297

non-increasing. Horn’s attainable region approach was further


revived in the mid-1990s by Glasser, Hildebrandt, Feinberg and 1
co-workers (Feinberg and Hildebrandt, 1997; Glasser et al., 1987;
Hildebrandt et al., 1990; Feinberg, 2000). Glasser et al. (1987) 0.8

Mole Fraction of B
proposed the concept of kinetically attainable region which is
realized through the processes of mixing and reaction by any 0.6
system of steady flow chemical reactors. Fienberg and co-workers
found attainable region for a reactor–separator system with 0.4
arbitrary separation efficiency but with constraints on operating
temperature, pressure, production of unwanted products, etc. 0.2 Increasing number
of stages
They solved the problem by a constrainted optimization techni-
que (Feinberg and Ellison, 2001; Tang and Feinberg, 2007). The AR 0
approach is further extended by others to reactive distillation 0 0.2 0.4 0.6 0.8 1
systems for some specific cases (Nisoli et al., 1997; Gadewar et al. Mole Fraction of A
2002; Agarwal et al., 2008a), which provided momentum for
setting ideal performance targets, and gave insight into the Fig. 1. (a) Multi-stage batch reactive rectification unit and (b) effect of number of
stages on attainable region for batch reactive rectification unit (Agarwal et al.,
synthesis problem by means of graphical visualization. Nisoli
2008a).
et al. (1997) formulated a systematic approach for reactor–
separator models, viz. CSTR/PFR with vapor removal, to identify
the feasible compositions that can be achieved in processes cases, selectivity factor, which is the ratio of desired reaction rate
combining reaction, mixing and separation. The extension of this to the undesired reaction rate, is proportional to (xA/xB) indicating
approach is proposed by Chadda et al. (2001) to devise basic that one should use distillation to attain high (xA/xB) ratio in the
building blocks such as co-current and countercurrent rectifying reactive zone. If A is more volatile than B, and if the reaction
or stripping cascades with liquid or vapor removal. Gadewar et al. mixture is non-azeotropic then the reaction may be performed in
(2002) further developed the models for a cascade of vapor–liquid a rectifying zone of RD column and catalyst may be placed
CSTRs, wherein, vapor and liquid flow counter-currently to each accordingly. In such case, one can use reactive rectification with
other. They showed that the AR analysis of conventional reactor minimum catalyst loading per stage and attain close to maximum
network can be conveniently extended to the reactor–separator yield that is defined by the stoichiometry as shown in Fig. 1, for a
systems. While this was an important step towards including RD specific case. If the reactant is least volatile then reactive stripping
into the family of other conventional reactors, there is a need to (not shown here) is recommended. All in all, this analysis provides
extend this approach further to identify various other RD models guidelines for selectivity maximization towards the desired product
which can work as building blocks in a network of reactors. We in case of non-azeotropic series and series–parallel reaction systems,
present such an attempt in this work. of which the selectivity factor and volatility patterns together would
This article is organized as follows: We begin with an intro- help one to decide the best configuration. Networking of reactors
duction to the previous work reported on selectivity engineering (including RD) is not necessary in such case and a single unit, if
with reactive distillation for simple reaction schemes, which designed properly, gives the desired selectivity.
forms the basis for further discussion. The van de Vusse reaction As mentioned before, it may be noted that this analysis was
scheme is then discussed in context to unique parameter, i.e. relatively straightforward because, based on the expression for
selectivity factor and the limitations, if any, in selectivity achieve- the selectivity factor (e.g. SF¼k1xA/k2xB, for a series reaction
ment. In the section that follows, we present the theory on scheme) and the knowledge of volatilities one can choose an
attainable region (AR) based on the reported literature on con- appropriate configuration. However, in an azeotropic system, the
ventional reactor network. The basic building blocks namely, presence of azeotrope restricts the separation thereby resulting in
continuous reactive condenser (CRC), and continuous reactive a lower selectivity to the desired product. In such cases, instead of
reboiler (CRR) and their cascade versions (CasCRC and CasCRR) reactive rectification or reactive stripping alone, it is their combi-
are introduced and elaborated. These models have the capability nation that may offer a better selectivity in some situations.
to surpass the performance of the conventional flow reactors Single reactant systems involving formation of azeotropes were
depending on the kinetics and vapor–liquid equilibria of a given subsequently analyzed in detail based on their respective residue
reaction system. The reaction-separation vectors are defined for curve maps, by Agarwal et al. (2008b). Further, the methodology
the newly defined models. Based on these vectors, we develop an was extended to azeotropic and non-azeotropic multi-reactant
algorithm for determining the desired network of newly intro- systems by Thotla and Mahajani (2009). In the case of azeotropic
duced RD models and conventional reactors. The influence of systems, the phase equilibrium compels one to opt for a network
various attributes such as volatility order and rate constants on of RD models for higher selectivity. The kinetics used in all the
AR is also discussed. previous examples was relatively simple and the schemes did not
The proposed algorithm can be extended to other multiple contain more than two reactions. In the present work, we have
reaction systems of which the selectivity parameter is a complex shown that even for ideal systems involving complex schemes
function of species concentrations. Being relatively simple in applic- one may need a network of RD models and conventional reactors
ability, these models help to identify the boundaries imposed by to expand the attainable region.
phase equilibrium and kinetics on AR prior to rigorous design,
simulation and optimization.
3. Complex reaction scheme: van de Vusse reaction

2. Reactive distillation for simple reaction schemes A class of challenging and essentially important problems in
conceptual design of RD column is that pertaining to multiple
In the previous work from our group, Agarwal et al. (2008a) series–parallel reactions, the so-called complex reactions. The van
presented the analysis of RD systems involving series (A-B-C) de Vusse reaction scheme (van de Vusse, 1964) is a classic
or series–parallel (2A-B; A þB-C) reactions. In each of these example of such reactions. The reaction rate vectors are expressed
V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297 2287

in terms of compositions as follows: 4. Attainable region approach


9
desired ðk1 Þ undesired ðk2 Þ undesired ðk3 Þ >
= In AR approach, every achievable set of compositions can be
A ! B ! C and 2A ! D,
ð1Þ realized by single or judicious combination of basic process units.
½rA rB rC rD  ¼ ½k1 xA 2k3 x2A ,k2 xB þ k1 xA ,k2 xB ,k3 x2A  >
;
Thus, for the given feed composition and reaction rate function, a
composition outside the attainable region cannot be realized in
In case of conventional reactor, the continuous flow reactors any steady state design such as PFR, CSTR, RD or their combina-
i.e., PFR and CSTR represent two conceptual extremes in reactor tions. In the following part of this section, we begin with the
operation. A PFR, in which ideally there is no back-mixing of attainable region approach used for the network of conventional
reactants, shows a higher yield of intermediate desired product in ideal reactors, i.e. CSTR and PFR. Then in the later sections, we
consecutive reaction systems. The CSTR, in which there is perfect apply the same logic for a larger family of reactors that includes
back-mixing, suppresses the side reactions that are of higher some representative RD models.
order than the one producing the desired intermediate product. It Simple steady state models for conventional isothermal and
is quite obvious to expect that there will be certain cases in which constant volume reactor are applied to construct the attainable
an intermediate level of mixing is preferred, whenever both region in the concentration space for reactor networks. They are
consecutive and higher order side reactions are occurring simul- as follows:
taneously. The reactor choice becomes difficult when both the
series and higher order parallel reactions occur simultaneously
as in the case of complex reaction scheme. Therefore, the CSTR xx0 ¼ trðxÞ ð3Þ
general guidelines for the selection of conventional steady state
reactor(s) do not apply to this scheme, thereby leaving further dx
PFR ¼ rðxÞ xðt ¼ 0Þ ¼ x0 ð4Þ
scope for networking. dt
Several researchers have suggested that yield of the desired
product B in the van de Vusse reaction scheme can be maximized where rðxÞ is a function of instantaneous species concentration
by some intermediate mixing as achieved in a recycle reactor or in given by reaction kinetics. As shown in Fig. 2a, both CSTR and PFR
a network of conventional reactors. Pasquali and Lelli (1974) trajectories are plotted by varying the only adjustable parameter,
studied column reactors (cascade of ideally mixed vessels with i.e. residence time (t). Convex hull, if any, is filled by drawing a
back-mixing between stages) that can be suitably used for the van straight line as shown in Fig. 2b. The composition on this straight
de Vusse reaction scheme to find the condition for maximum line may be achieved by mixing the two attainable compositions
yield. Similarly, Chitra and Govind (1981) studied the desired of the end points of this line. Further, the PFR vector defined by
product yield over a wide range of the rate constants, in a reactor Eq. (5) is plotted on every point of the boundary obtained. If the
system consisting of intermediate recycle stream. The effect of vector points outward then there is a scope to introduce a PFR at
variation in rate constants was studied by Gillespie and Carberry that point to expand the region further as shown in Fig. 2c
(1966). Lee (1977) demonstrated that the yield of the desired PR
product can be even higher if the recycle stream starts from some dxB uB rk ðxÞ
¼ PRk ¼ 1 ð5Þ
intermediate point along the reactor length. However, the product dxA k ¼ 1 A rk ðxÞ
u
yield was not optimized and the analysis was conducted for the
fixed values of the reaction rate constants and recycle ratio. Pahor
et al. (2000) combined the MINLP synthesis of reactor networks
with successive analysis in AR for improvement in overall process
performance. All in all, van de Vusse reaction is the model PFR PFR
CSTR
reaction that represents the class of complex schemes, which CSTR
Mole Fraction of B

Mole Fraction of B

need reactor networking to attain enhanced selectivity. Applica-


tion of reactive distillation for such reaction is not studied before
and is the main subject of this paper.
As we know, selectivity factor (SF), is defined as the ratio of
desired reaction rate to undesired reaction rate. This parameter is
expected to guide us on how one should manipulate the liquid
composition profile by using distillation attributes in RD column
for the maximization of selectivity towards the desired product.
Mole Fraction of A Mole Fraction of A
The selectivity factor (SF) in the case of van de Vusse reaction may
be defined as

rB k1 xA k2 xB k1 k2 ðxB =xA Þ


SF ¼ ¼ ¼ ð2Þ
Mole Fraction of B

Mole Fraction of B

rA k1 xA þ2k3 x2A k1 þ2k3 xA


CSTR
CSTR
It can be seen that the parameter SF is governed by both (xB/xA)
ratio and the absolute concentration of reactant A on the reactive PFR
PFR
stages. One has to minimize both (xB/xA) and xA to achieve high
selectivity. It is difficult to meet both these contradictory condi-
tions, simultaneously. Hence, unlike in simple reaction schemes,
one cannot take a quick decision only on the basis of selectivity
factor and relative volatilities. A network of RD configuration may Mole Fraction of A Mole Fraction of A
perform better than a single RD unit or a conventional reactor.
Fig. 2. Attainable region for PFR and CSTR for a van de Vusse reaction of arbitrary
Therefore, a systematic approach on the lines of attainable region kinetics: (a) PFR trajectory and CSTR locus, (b) convex hull on PFR and CSTR,
concept is necessary to be able to determine the achievable (c) PFR vectors on final attainable region and (d) PFR vectors on the PFR boundary
selectivity in such case. and CSTR vectors on its boundary and in complementary region to candidate AR.
2288 V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297

The region thus obtained is called as a candidate attainable The important assumptions made in development of model
region. Outside this region, CSTR vectors—i.e. PFR vectors (Eq. (5)) are that the reaction takes place only in the liquid phase and the
in opposite direction of the reaction path, are plotted at as many heat of reaction is negligible. Feeds, i.e. liquid for CRC and vapor
points as possible to ensure that none of them when extended for CRR are saturated and that the reaction rate constants are
intersects the candidate attainable region as shown in Fig. 2d. If insensitive to the change in temperature.
so, one may use a CSTR to attain such composition. If there is no The overall and component mole balances across the reactive
such vector then the candidate attainable region is the final condenser stage are given by
desired attainable region and the iterations are stopped.
X
R
In this procedure, PFR vector defined by Eq. (5) guides one to V1 L2 þ Wcat nT,k rk ðx2 Þ ¼ 0 ð6Þ
explore the possibility of expansion. Hence, if we intend to k¼1
introduce more RD configurations then the representative vectors
need to be defined for each individual configuration on similar X
R
V1 yi,1 L2 xi,2 þ Wcat ui,k rk ðx2 Þ ¼ 0 for i ¼ 1,2. . .,NC1 ð7Þ
lines. In the following sections, we introduce four basic RD models k¼1
and later define the corresponding vectors which can be used to
identify the potential of these configurations to be the part of the Dividing Eqs. (6) and (7) by feed flow rate F, we get
desired network for the given kinetics and volatilities. It may be V1 L2 XR

noted that the models defined here are only basic and they may  þ Da uT,k rk0 ðx2 Þ ¼ 0 ð8Þ
F F k¼1
not necessarily encompass the attributes of all the configurations
of reactive distillation. The main objective of this work is to XR
V1 L2
illustrate an approach which may further be extended to incor- yi,1  xi,2 þ Da ui,k rk0 ðx2 Þ ¼ 0 for i ¼ 1,2,. . .,NC1 ð9Þ
F F
porate various other RD models. k¼1

We would like to note here that though most of the time we use Here, Damkohler number, Dað ¼ kref Wcat =FÞ, is the ratio of
the term ‘‘attainable region’’ for the family of the reactors, some- characteristic liquid residence time to characteristic reaction
times, we use it for a specific individual reactor unit as well. For time; kref is rate constant for the reference reaction. Also, normal-
example, attainable region of CSTR means all the compositions that ized reaction rate, rk0 is the ratio of reaction rate to reference rate
can be achieved by a single CSTR and mixing streams. As we see constant ðrk =kref Þ, where rk is the actual reaction rate which is a
later, the complex reactors like reactive distillation has many function of instantaneous concentration, nT is the sum of the
parameters to play with. Hence, in this case, attainable region of a stoichiometric coefficient for the reaction and ni is the stoichio-
particular unit is the set of compositions that can be achieved by metric coefficient of component i. Now by combining Eqs. (8)
varying all the possible associated design parameters of that unit and and (9), we eliminate L2/F to get
by using mixing streams. The attainable region of a reactor family is
obviously larger than, or sometimes same as, that of a single unit. V1 XR
ðy x Þ þDa ðui,k xi,2 uT,k Þrk0 ðx2 Þ ¼ 0 for i ¼ 1,2,. . .,NC1
F i,1 i,2 k¼1
ð10Þ
5. Model development for new RD units
It should be noted that the rate of reaction is evaluated at the
Structurally, reactive distillation is not as simple as ideal condenser composition, which can be related to the outgoing
reactors like CSTR and PFR. Apart from residence time, there are composition by considering the overall and component mole
many other parameters such as feed location, number of stages, balances on non-reactive reboiler of Fig. 3a as shown below:
reflux ratio, reboil ratio, location and amount of side draw etc. FL1 þ L2 V1 ¼ 0 ð11Þ
that make the analysis more complicated. Hence, to begin with,
we define two basic models, viz. continuous reactive condenser Fxi,f L1 xi,1 þL2 xi,2 V1 yi,1 ¼ 0 for i ¼ 1,2. . .,NC1 ð12Þ
(CRC) and continuous reactive reboiler (CRR) as shown in Figs. 3a Dividing both the equations by feed flow rate F, the Eqs. (11)
and b, respectively. These configurations are the basic building and (12) can be expressed as
blocks of the network being formulated in the present work. In
CRC (Fig. 3a), the reboiler is non-reactive and the reaction takes L1 L2 V1
1 þ  ¼0 ð13Þ
place only in the condenser. The feed to the condenser (V1) is the F F F
enriched vapor which is in phase equilibrium with the liquid L1 L2 V1
leaving the reboiler. The entire unit may be considered as a CSTR xi,f  x þ x  y ¼0 for i ¼ 1,2. . .,NC1 ð14Þ
F i,1 F i,2 F i,1
with reaction taking place at composition resulting out of enrich-
By combining Eqs. (8), (13) and (14), the condenser composi-
ment due to one-stage distillation and the simultaneous reaction.
tion (xi,2) can be expressed in terms of other variables as
On the other hand, in CRR (Fig. 3b), only reboiler is reactive, which
receives feed in the form of condensed liquid (L1), which is in X
R
V1
equilibrium with the product vapor. xi,f xi,1 ðxi,1 xi,2 ÞDa uT,k rk0 ðx2 Þ þ ðx y Þ ¼ 0
k¼1
F i,2 i,1
for i ¼ 1,2,. . .,NC1 ð15Þ
Eq. (10) and (15) form the model for continuous reactive
Non-Reactive condenser (CRC). The set of these non-linear algebraic equations
2 Reactive can be solved to obtain the outlet composition. The model has
F 1
V y
V,y L ,x two important operating parameters, Da and V/F. For the given
V y L x
V/F, one can vary Da to cover the entire range of compositions.
F 1 L ,x Fig. 4a shows the profiles thus obtained for different values of V/F.
2
Reactive It can be seen that there is a minimum value of V/F below which
Non-Reactive
one cannot cover the entire composition range. This value
Fig. 3. Schematic diagram of (a) continuous reactive condenser (CRC) and (b) depends on the volatilities and kinetics. Above this V/F value,
continuous reactive reboiler (CRR). the performance is not much sensitive to the further change.
V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297 2289

As mentioned before, there is a critical value of V/F and L/F


0.25 beyond which no further improvement in performance is possi-
V/F = 100 ble. Hence, the region obtained at this critical values, can be called
V/F = 5 as attainable region for the respective models.
0.2
It is well known that PFR is the series network of large number
Mole Fraction of B

V/F = 2.5
of CSTRs with infinitesimally small volume or catalyst weight. If
0.15 we now consider the newly introduced units, i.e. CRC and CRR as
equivalent to CSTRs then their PFR equivalent configurations are
V/F = 1
the ones in which many such units with infinitesimally small
0.1 catalyst weights are connected in series as shown in Fig. 5. We
call these configurations as cascade of CRCs, i.e. CasCRC and
cascade of CRRs, i.e. CasCRR.
0.05
In CasCRC, the product from the non-reactive reboiler of the
first unit acts as a feed to the reboiler of the following unit in the
0 cascade and so on. The liquid phase reaction takes place in
0 0.2 0.4 0.6 0.8 1 reactive condenser. The vapor leaving the non-reactive reboiler
Mole Fraction of A of each unit is assumed to be in equilibrium with the liquid in the
respective reboiler. Similar logic can be applied for CasCRR.
The attainable regions for these two cascade models can now
0.16 L/F = 500 be easily obtained by solving the CRR and CRC models in series. It
is ensured that the Da per unit in this cascade is small enough so
that the region obtained is insensitive to further reduction in Da.
0.12 Again, the V/F and L/F ratios of small individual CRCs and CRRs are
Mole Fraction of B

L/F = 50
high enough so that the performance is insensitive to further
increase in these ratios. The regions thus obtained are shown in
0.08 Figs. 6a and b. It may be compared with the attainable regions of
L/F = 5 the CRC and CRR models given in Figs. 4a and b. It can be seen that
in certain composition range, the cascade models perform better
than the CRR and CRC models.
0.04
With the introduction of four new RD models, we now have six
L/F = 1 distinct reactor configurations, viz. CSTR, PFR, CRR, CRC, CasCRR

0
0 0.2 0.4 0.6 0.8 1
Mole Fraction of A 2 2 2
2

Fig. 4. Effect of V/F and L/F ratios for (a) CRC and (b) CRR models with van de Vusse L1,1 L1,2 L1,j-1 L1,j L1,N-1
k1 k2 k3
reaction, A!B!C, 2A!D. Rate constants, [k1 k2 k3]¼ [1 1 1] and relative
F 1 1 1 1 L1,N
volatilities, [aA aB aC aD] ¼[5 3 1 1].

V/F represents the fraction of the feed that is vaporized. It is


understandable that at lower values of V/F, only small amount of
feed is sent to the condenser wherein, the reactions are taking
place. Owing to this smaller fraction being subjected to the
reaction, one realizes a limit on the maximum possible conversion
that can be achieved in CRC. Hence, to determine the attainable
F L
boundary of the CRC model, we perform simulations at suffi-
ciently large value of V/F and vary Da to cover the entire
composition range for a given feed composition.
Continuous reactive reboiler (CRR) can also be modeled in a
V1,1 V1,2 V1,j-1 V1,j V1,N-1
similar way as the continuous reactive condenser (CRC) except
that the feed is in the vapor form and is introduced into the non- F 1 1 1 1 V1,N

reactive condenser (see Fig. 3b). The corresponding model equa-


tions are given below:
2 2 2 2

L1 X
R
ðx y Þ þDa ðui,k yi,2 uT,k Þrk0 ðx2 Þ ¼ 0 for i ¼ 1,2,. . .,NC1
F i,1 i,2 k¼1
ð16Þ

X
R
L1
yi,f yi,1 ðyi,1 yi,2 Þ þ Da uT,k rk0 ðx2 Þ þ ðy x Þ ¼ 0 F V
k¼1
F i,2 i,1

for i ¼ 1,2. . .,NC1 ð17Þ


The feasible regions for van de Vusse reaction system can be
obtained by increasing L/F to cover the entire span of product Fig. 5. (a) Cascade continuous reactive condenser (CasCRC) model and (b) cascade
composition as shown in Fig. 4b. continuous reactive reboiler (CasCRR) model.
2290 V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297

reaction path may work for CRC and CRR units, respectively. Let
0.35 us consider the CasCRC–CRC family given by Eqs. (10) and (15).
V/F = 50 The ratio of differential change in composition of B to the
0.3 differential change in composition of A for a CRC unit with
V/F = 0.5
infinitesimal value of Da may be given by Eq. (18) (refer Fig. 3
0.25
Mole Fraction of B

V/F = 0.2 for notations)


PR
0.2 DxB,1 ðuB,k uT,k xB,1 Þrk0 ðx2 Þ
V/F = 0.1 ¼ PRk ¼ 1 ð18Þ
DxA,1 0
k ¼ 1 ðuA,k uT,k xA,1 Þrk ðx2 Þ
0.15
To keep the calculations simple, since the change is very small,
0.1 it may be assumed that xf ¼ x1 and y1 ¼x2. Since y1 is the
composition of vapor in equilibrium with x1, x2 can be approxi-
0.05 mated as yf—a composition of vapor in equilibrium with the feed.
Based on these assumptions Eq. (18) takes a simple form as
0 PR
0 0.2 0.4 0.6 0.8 1 DxB,1 ðuB,k uT,k xB,1 Þrk0 ðyf Þ
CasCRC vector : ¼ PRk ¼ 1 ð19Þ
Mole Fraction of A DxA,1 k ¼ 1 ðuA,k nT,k xA,1 Þrk ðyf Þ
0

The expression is similar to that of the conventional reactor


0.24 except that the reaction rate is calculated at a vapor composition
L/F = 5 (yf) that is in equilibrium with the feed composition. Similarly, we
0.2 L/F = 1 can derive the expression of the vector for CasCRR–CRR family. It
is given by
Mole Fraction of B

0.16 PR
DyB,1 ðuB,k uT,k yB,1 Þrk0 ðxf Þ
CasCRR vector : ¼ PRk ¼ 1 ð20Þ
DyA,1 0
k ¼ 1 ðuA,k uT,k yA,1 Þrk ðxf Þ
0.12 L/F = 0.1
The compositions on the right hand side of the above equation
0.08 are obtained by VLE calculation. The only difference is that here
feed is vapor and the reaction rate is calculated at the corre-
L/F = 0.01 sponding liquid phase concentration (xf) that is in equilibrium
0.04
with the feed composition (yf).
The CRC and CRR vectors, which are positioned in the comple-
0 ment of candidate attainable region (say point P), can be eval-
0 0.2 0.4 0.6 0.8 1
uated using Eqs. (21) and (22). For CRC, the reaction terms on the
Mole Fraction of A right hand side are evaluated at the composition in equilibrium
Fig. 6. Effect of V/F and L/F ratios for (a) CasCRC and (b) CasCRR models with van with the composition at point P (i.e. xB,P) from which vector is to
k1 k2 k3 be drawn
de Vusse reaction, A!B!C, 2A!D. Rate constants, [k1 k2 k3] ¼ [1 1 1] and
relative volatilities, [aA aB aC aD] ¼ [5 3 1 1]. PR
xB,P xB,new ðuB,k uT,k xB,P Þrk0 ðyB,P Þ
CRC vector : ¼ PRk ¼ 1 ð21Þ
xA,P xA,new 0
k ¼ 1 ðuA,k uT,k xA,P Þrk ðyA,P Þ
and CasCRC, which can be the possible building blocks of the
However, it may be noted that the reaction in CRC takes place
network. It leaves us with a scope to extend the attainable region
not at the vapor composition in equilibrium with the product,
approach for conventional reactor network that includes these RD
models. It is therefore necessary to define appropriate vectors
corresponding to these units. In the next section, we derive the
expressions for these vectors. 0.25
CasCRC
PFR
0.2 CasCRR
6. Reaction-distillation vectors for the RD configurations
CRC
Mole Fraction of B

In the case of PFR (or series of CSTRs), the magnitude of


0.15
reaction vector is simply calculated as the ratio of net rate of CRR
formation of B to that of consumption of A (see Eq. (5)). These CSTR
rates are evaluated at a composition corresponding to the point 0.1
from which vector is to be plotted in the direction of the reaction
path, i.e. decreasing concentration of the reactant A. In the case of
CSTR, it is the same vector but plotted in the direction opposite to 0.05
the reaction path. The point from which we draw the CSTR vector
is a potential product composition. The PFR vector is positioned
on the boundary of the candidate attainable region whereas CSTR 0
vector is plotted at as many points as possible in the complement 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
of the candidate attainable region. Mole Fraction of A
This means, for the four additional RD units, we need to define
Fig. 7. Comparative attainable regions for conventional reactor (PFR & CSTR),
two basic vectors, one for the CasCRC and the other one for the CasCRC, CasCRR, CRC and CRR for the van de Vusse reaction,
CasCRR unit. The same vectors when plotted in the complement k1 k2 k3
A!B!C, 2A!D with rate constants, [k1 k2 k3]¼ [1 1 3] and relative
of the candidate attainable region in the opposite direction of the volatilities, [aA aB aC aD] ¼[5 3 1 1].
V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297 2291

but at the composition of the stream leaving the reactive it happens to be the one calculated at the vapor composition in
condenser. Unlike in its cascade version, the Damkohler number equilibrium with xB,P (point P), which acts as feed to the reactive
of the condenser may not be small enough and x2 may be much condenser. This concept is elaborated in Appendix A. Similar logic
different than y1 (see Fig. 3a). Hence, in a true sense, there exist can be applied for CRR vector and it may be evaluated using
many CRC vectors corresponding to different values of x2 PR
yB,P yB,new ðuB,k uT,k xB,P Þrk0 ðxB,P Þ
obtained by varying Da of the reactive condenser. As explained CRR vector : ¼ PRk ¼ 1 ð22Þ
yA,P yA,new 0
k ¼ 1 ðuA,k uT,k xA,P Þrk ðxA,P Þ
in Appendix A, out of all these vectors, the steepest one with
negative slope is to be chosen and incidentally, in our case, Hence, in the present case, while evaluating CRC and CRR
vectors, we have applied the same logic as that of CSTR. In short,
CRC and CRR vectors are the vectors of their cascades (Eqs. (19)
0.25 and (20)) drawn in opposite direction of the reaction path from a
CasCRC point outside the candidate attainable region.
E D
0.2
C
7. Algorithm for RD model network
Mole Fraction of B

PFR
0.15 In this section, we propose an algorithm to obtain the attain-
CasCRR
able region and the corresponding network that may include all
the six possible configurations. For illustration purpose, a simpli-
0.1 B fied van de Vusse scheme (Eq. (1)) with rate constants, [k1 k2
k3]¼[1 1 3] and volatilities as [aA aB aC aD]¼[5 3 1 1] is chosen.
CRR
The feed is pure reactant A.
0.05

(i) Construct the boundaries for all the six reactor models. PFR
0O and CSTR boundaries are generated by varying the residence
A time. As discussed before, in the case of CRC and CasCRC
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
models suitable values of V/F is chosen and in the case of CRR
Mole Fraction of A
and CasCRR models, suitable value of L/F is chosen such that
Fig. 8. Candidate AR with convex hull on non-convex portion. entire span of reactor composition is covered by varying Da.

0.25 0.25
E E D
D
0.2 0.2 C
C
Mole Fraction of B
Mole Fraction of B

0.15 CasCRR
Boundary
0.15 CasCRR
Boundary

0.1 B
CasCRC B 0.1 CasCRC
Boundary Boundary

0.05 0.05
CRR CRR
Boundary Boundary

0O 0O
A A
0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1
Mole Fraction of A Mole Fraction of A

0.25
E D
0.2 C
Mole Fraction of B

0.15 CasCRR
Boundary

0.1 B
CasCRC
Boundary
0.05
CRR
Boundary
0
O A
0 0.25 0.5 0.75 1
Mole Fraction of A
Fig. 9. Cascade model vectors on candidate AR. (a) Direction of CasCRR vectors, (b) direction of CasCRC vectors and (c) direction of PFR vectors.
2292 V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297

The corresponding boundaries thus generated for the repre- 1


sentative system are shown in Fig. 7. Vector Notation
(ii) Construct the convex hull wherever possible. It is shown by CRR
the dashed line segment AB, BC CD and DE, respectively, in 0.8 CSTR
Fig. 8. Thus, a candidate attainable region ABCDEO is
CRC
generated.

Mole Fraction of B
(iii) The candidate AR is then tested to ensure that none of the
three rate vectors corresponding to PFR, CasCRC, CasCRR, 0.6
positioned on the boundary, points outward. As explained
before, if there exist such vectors then candidate AR can be
extended further by introducing the corresponding reactor 0.4
model. Fig. 9a–c show all the three vectors ploted on the
boundary obtained in the previous step.
The region bounded by mixing line AB is convex with CasCRR 0.2
vector pointing inwards. However, CasCRR vectors on the
segment BC formed by the union between CRR and CasCRR
are also pointing outwards (Fig. 9a), hence it is possible
that CasCRR model with feed point on convex hull BC can 0
0 0.2 0.4 0.6 0.8 1
enlarge the candidate AR. Similarly, CasCRC vectors on the
convex hull between CasCRC and PFR (segment DE), PFR and Mole Fraction of A
CasCRR boundaries (segment CD), respectively (Fig. 9b) are
Fig. 12. Vectors corresponding to conventional CSTR, CRR and CRC shown in outer
pointing outwards thereby inviting further expansion of region to attainable region.
candidate AR by CasCRC model with feed point on CasCRR
trajectory.

0.3
CasCRC 0.8
H
0.25
Mole Fraction of B
Mole Fraction of B

0.2 0.6
F G

0.15 Convex hull


0.4
on CRR
CasCRC
0.1 H
B
0.2
0.05 CasCRR Y
B
X

0 0
O A O A
0 0.2 0.4 0.6 0.8 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole Fraction of A Mole Fraction of A
k1 k2 k3
Fig. 10. The enhanced candidate attainable region obtained by filling the non- Fig. 13. Final attainable region for van de Vusse reaction, A!B!C, 2A!D
convexity between (a) CasCRR and CRR and (b) CasCRR and CasCRC trajectory, with rate constants, [k1 k2 k3] ¼[1 1 3] and relative volatilities, [aA aB aC aD]¼
respectively. [5 3 1 1].

1 1

0.8 0.8
Mole Fraction of B
Mole Fraction of B

0.6 0.6

0.4 0.4
H H
G G
0.2 0.2
B B

0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Mole Fraction of A Mole Fraction of A

Fig. 11. The candidate attainable region with (a) CasCRR vectors and (b) CasCRC vectors on its boundary.
V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297 2293

Table 1
Attainable regions for different relative volatilities and rate constants [a1(¼k3/k1) a2(¼ k2/k1)].

Rate constants: [a1 a2] ¼[1 1] Rate constants: [a1 a2] ¼ [0.05 0.5] Rate constants: [a1 a2] ¼ [0.5 0.05]

Relative volatilities [5 3 1 1]

Relative volatilities [5 3 1 5]

Relative volatilities [5 1 1 1]

Rate constants: [a1 a2] ¼[1 1] Rate constants: [a1 a2] ¼ [0.05 0.5] Rate constants: [a1 a2] ¼ [0.5 0.05]

Relative volatilities [5 5 1 1]
2294 V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297

Table 1 (continued )

Rate constants: [a1 a2] ¼[1 1] Rate constants: [a1 a2] ¼[0.05 0.5] Rate constants: [a1 a2] ¼ [0.5 0.05]

Relative volatilities [5 5 1 5]

Relative volatilities [1 3 5 1]

Rate constants: [a1 a2] ¼[1 1] Rate constants: [a1 a2] ¼[0.05 0.5] Rate constants: [a1 a2] ¼ [0.5 0.05]

Relative volatilities [1 3 5 5]

Relative volatilities [1 5 1 1]
V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297 2295

Table 1 (continued )

Rate constants: [a1 a2] ¼[1 1] Rate constants: [a1 a2] ¼ [0.05 0.5] Rate constants: [a1 a2] ¼ [0.5 0.05]

Relative volatilities [1 3 1 5]

Rate constants: [a1 a2] ¼[1 1] Rate constants: [a1 a2] ¼ [0.05 0.5] Rate constants: [a1 a2] ¼ [0.5 0.05]

Relative volatilities [5 3 5 1]

Relative volatilities [5 5 5 1]

(iv) CasCRR is introduced at point B, i.e. the first point on the The final AR (ABGHO) thus obtained for the system of interest
candidate AR, when the search started in a direction away is shown in Fig. 13. For comparison purpose, the AR for conven-
from the feed A, at which vector starts pointing outward. tional reactor AXYO is also shown along with the final AR for RD
Similarly, CasCRC is introduced at point G. We obtain the new models. The AXYO boundary is obtained by the procedure out-
boundaries as shown in Fig. 10. If the boundary obtained is lined before for the conventional reactor network. It may be
not convex then go to step (ii). concluded that inclusion of RD in the family of reactors has
(v) The boundary obtained in Fig. 11 is the one on which all the helped to expand the attainable region.
vectors either point inward or they are tangents (see Fig. 11).
To explore the further possibility of the expansion of candi-
date AR, construct CSTR, CRC and CRR vectors, i.e. the vectors 8. RD networks for different kinetics and volatility patterns
drawn in the opposite direction of the reaction path, outside
the candidate region as shown in Fig. 12. If these vectors The relative volatilities and kinetic rate constants play a major
(CSTR, CRC, and CRR) when extended, do not point back into role in deciding the appropriate RD network configurations. If the
it, the current limits form the boundary of the desired AR and rate constant k3 is much smaller than k2, then van de Vusse reaction
the procedure terminates. behaves like simple series reaction and the design methodology for
2296 V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297

the same as mentioned by Agarwal et al. (2008a). One the other CasCRR cascade continuous reactive reboiler
hand, if rate constant k3 is much larger than k2, this reaction scheme CRC continuous reactive condenser
is equivalent to parallel reaction system. It is possible that variation CRR continuous reactive reboiler
in rate constants may eliminate the cross-over in AR and a single RD CSTR continuous stirred tank reactor
model may suffice. The effect of relative volatility and rate constants Da Damkohler number
on the AR and corresponding network is summarized in Table 1. PFR plug flow reactor
The new networks derived based on the proposed algorithm
surpass the kinetics constraints imposed by the conventional reactor Graphical symbols
networks. It is clear that for van de Vusse reaction operated in a
kinetic regime, simultaneous distillation has a capability to improve
plug flow reactor
the performance. There is a further scope to make distillation
efficient by increasing number of stages (e.g. the configuration such
as reactive rectification shown in Fig. 1) or using multi-feed, multi- continuous stirred tank reactor
product configurations to suit our requirement. This will be an
obvious extension of the work presented in this paper.
continuous reactive condenser

9. Conclusions

It is well known that RD holds potential of adjusting the


species compositions in the reactive zone for selectivity max- continuous reactive reboiler
imization. In the present work, attainable region approach, which
is already established for conventional reactor network is
extended further to include few representative RD configurations.
Four structurally different RD configurations are introduced and cascade continuous reactive condenser
the corresponding vectors are defined. The vectors indicate the
need of RD model networking to enlarge the set of attainable
compositions. RD models and their network perform better than
their conventional reactors and their network. It must be noted cascade continuous reactive reboiler
here that we have introduced only four structurally different
models of RD in the family of reactors. With more models (e.g.
multi-stage units, multi-feed units, side draw, etc.), additional
parameters will emerge and provide opportunities to further
expand the attainable region obtained in the present work.
Appendix A. CRC and CRR vectors

There is a basic difference in the calculation for CRC or CRR


Nomenclature vector and that for conventional CSTR. CSTR has a unique property
that the mixing vector obtained by joining inlet and outlet composi-
a1 and a2ratio of rate constants viz., k3/k1 and k2/k1, respectively tions is collinear with the rate vector evaluated at the reactor exit
F feed flow rate (mol/s) concentration and hence the CSTR vector is exactly opposite of the
k rate constant PFR vector. However, in the case of CRC, the rate vector has to be
N number of CRC or CRR units in the cascade evaluated at the composition of condenser wherein reaction takes
NC number of components place, and the mixing vector is evaluated at the composition of the
rk reaction rate for kth reaction, mole/(time  mass of reboiler, i.e. the outlet stream. Hence, the mixing and rate vectors for
catalyst) CRC are not collinear. Thus, unlike in the case of conventional
R total number of reactions reactor vectors, CRC vector is not exactly opposite of its differential
V and L vapor and liquid flow rate respectively (mol/s) counterpart, i.e. CasCRC vector. Here, we throw some light on this
Wcat mass of catalyst aspect in context of the proposed algorithm.
xi and yi mole fraction of ith component in liquid and vapor Having achieved the candidate attainable region that fulfils the
phase, respectively necessary conditions for the convexity of AR (i.e. after step (v) in the
a relative volatility algorithm), the CRC and CRR vectors need to be constructed in the
n vector of stoichiometric coefficients in reaction space outside this region. This step ensures that there is no further
t mean residence time (s) scope for the expansion of AR. Let us consider point P in the
complement of AR (see Fig. A.1). We would like to know whether
Subscripts this composition can be attained by a CRC with feed of any
composition inside the candidate attainable region. One should thus
A, B, C, D components involved in reaction evaluate the rate vector (Eq. (A.1)) at the reactive condenser
cat catalyst composition P1 and draw it from point P in the opposite direction
i ith component of the reaction path
ref reference component PR
xB,P xB,new ðuB,k uT,k xB,P Þrk0 ðxP1 Þ
¼ PRk ¼ 1 ðA:1Þ
xA,P xA,new 0
k ¼ 1 ðuA,k uT,k xA,P Þrk ðxP 1 Þ
Abbreviations
Now as shown in Fig. A.1, we can consider reactive condenser
AR attainable region as a CSTR with feed Pe and product P1. Pe is the composition of
CasCRC cascade continuous reactive condenser vapor in equilibrium with the CRC product, i.e. P. Thus we can
V. Amte et al. / Chemical Engineering Science 66 (2011) 2285–2297 2297

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