Chemical Engineering and Processing 81 (2014) 1–12

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

Catalytic cyclic distillation – A novel process intensification approach

in reactive separations
Cătălin Pătruţ a , Costin Sorin Bîldea a,∗ , Anton A. Kiss b,∗∗
a
University “Politehnica” of Bucharest, Department of Chemical and Biochemical Engineering, Polizu 1-7, 011061 Bucharest, Romania
b
AkzoNobel – Research, Development & Innovation, Zutphenseweg 10, 7418 AJ Deventer, Netherlands

a r t i c l e i n f o a b s t r a c t

Article history: Cyclic distillation uses a periodic operation mode that leads to key benefits, such as increased column
Received 7 February 2014 throughput, lower energy requirements and much higher separation performance. By integrating chem-
Received in revised form 12 April 2014 ical reactions with cyclic distillation, a novel process intensification approach is possible – catalytic cyclic
Accepted 12 April 2014
distillation – which outperforms classic reactive distillation.
Available online 21 April 2014
This paper is the first to describe the catalytic cyclic distillation process and to develop a rigorous
mathematical model. By means of a case study involving a simple reaction system, the model is used
Keywords:
to demonstrate the key benefits of this operation mode. In addition, the synthesis of dimethyl ether by
Reactive separation
Process intensification
catalytic cyclic distillation is considered, for which a design algorithm is suggested. Investigation of the
Process design column behavior reveals the coexistence of two periodic states, one of them being unstable.
Case studies © 2014 Elsevier B.V. All rights reserved.
Dimethyl ether

1. Introduction proven technology – with well-developed methods for the process

Reactive distillation (RD) – also known as catalytic distillation,
when a solid catalyst is used –is a process intensification approach
that integrates reaction and separation into a single unit allow-
ing the simultaneous production and removal of products, thus
improving selectivity and productivity, reducing the energy use
and the need for solvents, ultimately leading to high-efficiency sys-
tems with green engineering attributes [1,2]. Some of the benefits
of reactive distillation are realized by using reaction to improve sep-
aration, while others are attained by using separation to improve
reactions – the maximum effect being achieved when both aspects
are important. Nevertheless, the application of RD is somewhat
limited by constraints, such as common operating range for distilla-
tion and reaction, proper boiling point sequence, providing proper
residence time characteristics and more difficult control [2–5].
Remarkable, reactive distillation has found many important
industrial applications during the past decades, such as methyl
tert-butyl ether (MTBE), ethyl-tert butyl ether (ETBE), tert-amyl
methyl ether (TAME), fatty acid methyl esters (FAME) and methyl
acetate, to name just a few [1,2,6–8]. Nowadays RD is considered
∗ Corresponding author. Tel.: +40 21 402 3903; fax: +40 21 318 5900.
∗∗ Corresponding author. Tel.: +31 26 366 9420; fax: +31 57 067 9125.
E-mail addresses: s bildea@upb.ro (C.S. Bîldea), Tony.Kiss@akzonobel.com,
tonykiss@gmail.com (A.A. Kiss).
synthesis, design, control and simulation [2,9–12].
Periodic (cyclic) operation is another intensification technique
which can be used to enhance processes such as liquid–liquid
extraction [13], particle separation [14], absorption [15], crystal
purification [16] and (chromatographic) chemical reaction [17,18].
In distillation technology, the periodic operation was suggested by
Cannon [19] and applied to columns with various tray types, such
as sieve and screen [20], packed-plate [21], and bubble cap [22].
A distillation cycle consists of a vapor-flow period and a liquid-
flow period. During the vapor-flow period, the liquid is stationary
on the trays and the vapor is flowing inside the column from
reboiler to condenser. During the liquid-flow period, the flow of
vapor is stopped and the liquid is moved between the trays. No
downcomers are needed for this type of operation; therefore the
plates are simpler, cheaper and more flexible. Moreover, because
there is no mixing of liquid of different concentration, the perfor-
mance of the distillation unit is increased [23]. For example, in a
five-stage column used to separate a water-methanol mixture, the
vapor flow-rate required for a cyclic column was only 50–80% of
the vapor flow-rate required in a conventional distillation column
where the same separation is achieved [24]. A semi-plant distilla-
tion column with 15 stages, separating a water–acetone mixture
showed a 250% capacity increase [25]. However, experiments
[25,26] and simulation [27] showed that, due to hydrodynamic
problems, the tray design must be modified or a pressure equaliz-
ing manifold should be installed when more than 12 trays are used.

http://dx.doi.org/10.1016/j.cep.2014.04.006
0255-2701/© 2014 Elsevier B.V. All rights reserved.
2 C. Pătruţ et al. / Chemical Engineering and Processing 81 (2014) 1–12

Fig. 1. Working principle of cycling distillation using trays with sluice chambers.

Practical solutions such as external pressure-equalizing manifolds to limited accuracy of the results. This work fills this gap by develop-
[28], composite schemes [23] and stepwise periodic operation [55] ing a rigorous mathematical model of catalytic cyclic distillation. By
were proposed. A breakthrough was recently achieved when a new means of a case study involving a simple reaction system, the model
type of trays especially designed for cyclic operation was invented is used to demonstrate the key benefits of the cyclic operation
[29,30]. The special trays (Fig. 1) are provided with valves and mode. In addition, the synthesis of dimethyl ether (DME) by cat-
sluice chambers located under the trays. The operation principle is alytic cyclic distillation is considered – for which a process design
the following: during the vapor-flow period, the valves are closed algorithm is proposed and the column behavior is investigated in
and the liquid stays on the tray. During the liquid-flow period, the terms of state multiplicity.
valves open and the liquid flows from the tray to the sluice chamber
below. When another vapor-flow period begins, the sluice chamber
3. Results and discussion
is opened and the liquid flows to the empty tray below. It is worth
noting that by using this type of tray there are no complications
3.1. Mathematical model
related to the increased number of trays.
The advantages of cycling distillation were also implemented
The mathematical model for the catalytic cyclic distillation
at industrial scale using trays provided with sluice chambers. In
columns was developed taking into account the following realistic
the food industry (Lipnitsky Alcohol Plant, Ukraine), a 20,000 L/day
assumptions:
cyclic distillation column is used to increase the alcohol concen-
tration from 3.29 mol% to 18.25 mol%. Moreover, a column used
1. Vapor–liquid equilibrium is reached on every stage.
for concentrating impurities, also part of Lipnitsky Alcohol Plant
2. The vapor holdup can be neglected.
in Ukraine is also cyclically operated [29].
3. On each stage the liquid is perfectly mixed.
Several models are available to simulate the behavior of
4. The column is fed with saturated liquid.
(non-catalytic) cyclic distillation columns. Initially, the models
5. The movement of the liquid from one tray to another is instan-
considered only binary mixtures and employed drastic simpli-
taneous.
fying assumptions such as linear equilibrium, infinite reboiler
and negligible condenser holdup [23,28,31–33]. These simplified
assumptions were relaxed by recent studies [29,34,35] that pro- It should be noted that no assumptions were made regarding the
vided more realistic models. Non-iterative design algorithms were linearity of the vapor–liquid equilibrium (VLE), the size of reboiler
suggested and applied for binary mixtures with non-linear equilib- and condenser holdups and the number of components present in
rium [34,36]. the system.

3.1.1. Vapor-flow period

2. Problem statement The mass balance equations describe the evolution of tray-
holdup for each component j = 1,NC, as follows
The advantages of cyclic operation of distillation columns
compared to steady state operation are: higher capacity, higher dM1,j
Condenser : = V2 · y2,j (1)
flexibility and lower energy requirements [4,29]. The benefits of dt
combining reaction with distillation into a single device are also
well known: higher conversion can be obtained in more compact dMk,j
unit and potential difficult separations that arise due to azeotropic Trays : = Vk+1 · yk+1,j − Vk · yk,j + j · rk · mk ,
dt
mixtures can be avoided. Even if catalytic distillation is a proven
technology and cyclic operation was demonstrated at industrial k = 2, NT − 1 (2)
scale, to the best of our knowledge, no paper that investigates
the behavior of a catalytic distillation column operated in periodic
cycles was published until now. dMNT,j
Reboiler : = −VNT · yNT,j (3)
Various simulation and design models of conventional catalytic dt
distillation can be obtained by simply adding a reaction term to a
The simplified energy balance describes the changing of the
distillation model; therefore, rigorous simulation is possible using
vapor flow-rate along the column due to reaction heat and different
commercial software such as AspenTech Aspen PlusTM . A similar
components heat of vaporization:
approach to modeling the catalytic cyclic distillation is hampered
by the fact that most of the models for cyclic distillation were devel-

Vk+1 · 
j k,j
· yk+1,j + rk · mk · r Hk
oped at a time when the available computing power was low and Vk =  (4)

j k,j
· yk,j
expensive. Consequently, they employ drastic assumptions leading
 C. Pătruţ et al. / Chemical Engineering and Processing 81 (2014) 1–12 3

For each tray, k = 1. . .NT, the following relationships describe the 3.1.3. Solution method
liquid–vapor equilibrium: The Eqs. (1)–(14) can be written in the following condensed
form, where ˚(V) and ˚(L) are the mappings relating the system
Mk,j
xk,j =  j = 1, NC (5) state at the start and the end of the vapor-flow and liquid-flow
j
Mk,j periods, respectively:

P · yk,j − xk,j · k,j (x1 , . . .xNC , Tk ) · Pj

vap
(Tk ) = 0, j = 1, NC (6) M(L) = ˚(L) (M) (22)
 M (V )
=˚ (V )
(M) (23)
yk,j − 1 = 0 (7)
j
The periodicity condition requires:
(V )
M = ˚(V ) ◦ ˚(L) (M(V ) ) (24)
The initial condition specifies the state of the system at the
beginning of the vapor-flow period, which is the same as the state A straightforward solution of (24) can be obtained by consid-
at the end of the liquid-flow period: ering an initial state and applying relations (22) and (23) until the
difference between two iterations becomes lower than a given tol-
M(t = 0) = M(L) (8)
erance. However, this direct-substitution method converges only
Knowing the reboiler vapor flow rate VNT and the duration of if the periodic state is stable. The convergence properties can
the vapor-flow period tvap , the state of the system at the end of the be improved by considering M(V) as the unknowns in the sys-
vapor-flow period can be found by integrating the Eqs. (1)–(7) with tem described by Eq. (24), which is solved by numerical methods
the initial condition (8) specific to nonlinear algebraic equations. Alternatively, one can
view the model of catalytic cyclic distillation as a boundary value
M(V ) = M(t = tvap ) (9) problem, where the differential equations and (the non-separated)
boundary conditions are given by vapor- and liquid-phase models,
3.1.2. Liquid-flow period respectively. Such problems can be effectively solved by various
The liquid-flow period equations describe the movement of the numerical techniques, for example (multi) shooting methods or
liquid from one tray to the tray below, the product removal and the orthogonal collocation on finite elements.
mixing that occurs at the feed and inside the reboiler. The following In this work, we used the variable coefficient DVODE solver [37]
equations give, for each component j = 1,. . .,NC the stage holdup at – a variable-coefficient ODE solver with fixed-leading-coefficient
the end of the liquid-flow period: implementation – to integrate the vapor-phase differential equa-
tions, and the NLEQ1 solver [38] – using global Newton method
(L) (V ) (V )
Condenser : M1,j = M1,j − (D + L) · x1,j (10) with error oriented convergence criterion – to find the solution
of the algebraic equations. The solution dependence versus one
(L) (V )
First tray : M2,j = L · x1,j (11) parameter was traced using PITCON, which implements a local
parameterization continuation algorithm [39,40,41]. Design of the
(L) (V )
Feed tray : MNF+1,j = MNF,j + F · xF,j (12) catalytic distillation column required solving delay-differential
equations (DDE) with events and discontinuities in model parame-
(L) (V )
Trays : Mk,j = Mk−1,j k = 2, NT − 1, k =
/ NF (13) ters and state variables, for which efficient numerical methods can
be found in the literature [42,43].
(L) (V ) (V ) (V )
Reboiler : MNT,j = MNT,j − B · xNT,j + MNT −1,j (14)
3.2. Benefits of cyclic operation
Inventory control requires the specification of the total con-
denser and reboiler holdups at the end of the liquid flow period, In this section, a simple case study is used to prove the advan-
HC and HB . Then, knowing the reflux L, the amount of distillate D tages of cyclic operation when applied to catalytic distillation. The
and bottoms B can be calculated. Alternatively, one can specify the reaction system described by Eq. (25) involves a middle boiling
distillate D and calculate the reflux L from Eq. (15). reactant B, while the products A and C are the components with
 (V )
the highest and the lowest relative volatility, respectively.
HC = M1,j − L − D (15)
j=1,NC
2B  A + C (25)
 (V )
The stoichiometry of this chemical reaction is rather similar to
HB = MNT,j − B (16) 2-pentene metathesis leading to 2-butene and 2 hexene, which was
j=1,NC earlier considered in several catalytic distillation studies [44–47].
The reactant consumption rate is given by:
Note that, when the assumption of constant vapor flow is valid  
(Vk = V, k = 2,. . .,NT), the condenser and reboiler mass balance over xA xC
r =k· xB2 − (26)
one cycle can be written as: Keq
V · tvap = D + L (17) where the reaction rate constant was considered temperature-
independent k = 0.06 kmol/min/kgcat and the equilibrium constant
L + F = V · tvap + B (18)
is Keq = 0.25.
Leading to the following feasibility condition: The relative volatilities were considered to be constant and
equal to: ˛AB = 3 and ˛BC = 3. Therefore, the vapor phase mole frac-
L < V · tvap < L + F (19) tions are given by:
xk
Moreover, the tray holdups are: yk =  (27)
j
˛jk xj
Mk = L, k = 2, . . ., NF (20)
The model was simplified by considering that the components
Mk = L + F, k = NF + 1, . . .NT − 1 (21) have equal heat of vaporization and that the reaction heat can be
4 C. Pătruţ et al. / Chemical Engineering and Processing 81 (2014) 1–12

that can effectively replace chloro-fluoro-carbons. Conventionally,

high purity DME is synthesized by the dehydration of methanol
produced from syngas, in a process involving a catalytic fixed-bed
reactor followed by a direct sequence of two distillation columns
used for the DME separation and methanol recovery [50].
Note that the DME synthesis by reactive distillation was the sub-
ject of several recent papers [48–50]. One mole of DME is obtained
from 2 moles of methanol – while water is formed as a secondary
product.

2CH3 OH  H3 C − O − CH3 + H2 O (32)

3.3.1. System properties

Because water, DME and methanol form a non-ideal mixture, the
vapor–liquid equilibrium (VLE) was described using the Raoult’s
Fig. 2. Comparison of vapor to feed ratio necessary to achieve given product purity
in conventional and catalytic cyclic distillation. law amended with activity coefficients given by Eq. (6) The tem-
perature on each tray was determined as the boiling temperature
of the mixture on tray, according to the Eqs. (6) and (7). The
neglected. The consequences of these assumptions are constant
vapor pressures follow the extended Antoine Eq. (33), with the
vapor flow-rate along the column and constant liquid holdup dur-
coefficients C1 –C7 taken from Aspen Plus [51] and conveniently
ing the vapor-flow period.
presented in Table 1.
To prove the advantages of the cyclic operation, a mathematical
 C2

model for a conventional catalytic column was written, using the
Pvap = exp C1 + + C4 · T + C5 · ln(T ) + C6 · T C7 (33)
same assumptions. The steady state mass balance equations are T + C3
given by relations (28)–(31):
For the activity coefficients, the Wilson model – Eqs. (34) and
Condenser : V · y2,j − (L + D) · x1,j = 0 (28) (35) – was used. The values of the binary interaction parameters
ai,j and bi,j (Table 2) were found by regression of experimental data
Trays : L · (xk−1,j − xk,j ) + V · (yk+1,j − yk,j ) + j · rk · mk = 0 (29) published in literature [52]. Fig. 3 conveniently compares the exper-
imental [52] and simulation results of VLE calculations using the
Feed tray : F · (xF,j − xNF,j ) + L · (xNF−1,j − xNF,j ) Wilson model with regressed parameters, a very good agreement
being observed.
+ V · (yNF+1,j − yNF,j ) + j · rNF · mNF = 0 (30)
⎛ ⎞
  Aj,i
ln(i ) = 1 − ln ⎝ Ai,j · xj ⎠ −  (34)
Reboiler : (L + F) · xNT −1,j + V · yNT,j − B · xNT,j = 0 (31) A · xk
k j,k
j j

Fig. 2 compares the vapor to feed ratio V/F needed to obtain given
1
distillate purity xA,D in conventional and catalytic cyclic distillation ln(Ai,j ) = ai,j + bi,j · (35)
T
columns with equal number of stages in the rectifying, reactive and
stripping zones. The amount of catalyst was taken as mk = 10 kg per It is well known that the Wilson model cannot predict the exist-
reactive stage. In all cases, 2.5 kmol/min of reactant B are fed on the ence of two immiscible liquid phases, while DME is immiscible with
middle stage. water. However, the data presented in literature [53] show that
It can be observed that for the same vapor flow-rate, which only one liquid phase exists at 313 K, if the methanol mole fraction
is related to the energy requirement, much higher purity can be exceeds 0.07. This condition is fulfilled, as the mixture contains
obtained by cyclic operation. For example, cyclic operation of a 9- mainly water and methanol in the stripping section, methanol and
stage column with V/F = 3 gives a product purity xA,D = 0.9, while DME in the rectifying section, and the mole fraction of methanol is
the purity is only xA,D = 0.8 for steady state operation. Moreover, far larger than 0.07 along the reaction zone. Therefore, the Wilson
if the same purity must be obtained, the cyclic column requires model with regressed activity coefficients parameters appropri-
less stages and a smaller vapor flow-rate. For example, a distillate ately describes the phase equilibrium in the considered reactive
purity of 0.99 can be achieved using a column with 15 stages oper- distillation column.
ated cyclically with a V/F ratio of about 1.8. Using a conventional The reaction kinetics [54] describes the liquid phase methanol
column with 15 stages, the V/F ratio should be almost three times dehydration to DME on Amberlyst 35:
higher. Finally, the cyclic column is more flexible: the column with k
15 stages can be used for a much wider range of product purities rDME = 2
(36)
(1 + (KW /KMeOH ) · (CW /CMeOH ))
when operated in a cyclic manner. It should also be remarked that
flooding would prevent a conventional column which was designed
 −98, 000 
k = 6.12 × 107 · exp kmol/(s kgcat ) (37)
for xA,D = 0.9 (V/F = 1.8) to deliver more pure products (xA,D = 0.99, 8.31 · T
V/F = 5), while no such constraints occur for cyclic operation.
KW
 2964

= exp −6.46 + (38)
KMeOH T
3.3. Case study: dimethyl-ether synthesis
The reaction enthalpy was considered to be constant.
After proving the advantages of catalytic cyclic distillation com- Its value was calculated at 400 K in liquid phase to be
pared to conventional catalytic distillation, this section describes r H = –1911.15 kJ/kmol [51]. The vaporization enthalpy (kJ/kmol)
the application of this technique to the synthesis of dimethyl ether of the components [51] is given by Eq. (39). The values of the param-
(DME). DME is of great industrial interest due to its use as clean eters required in Eq. (39) are given in Table 3 [51].
fuel for diesel engines or in combustion cells, as a precursor to 2 3
other organic compounds, as well as a green aerosol propellant  = C1 · (1 − Tr )(C2 +C3 ·Tr +C4 ·Tr +C5 ·Tr ) (39)
 C. Pătruţ et al. / Chemical Engineering and Processing 81 (2014) 1–12 5

Table 1
Extended Antoine coefficients for methanol, water and DME.

C1 C2 C3 C4 C5 C6 C7 Range of validity

Methanol 71.205 −6904.5 0 0 −8.8662 7.4664 × 10−6 2 175.5 < T < 512.5
Water 62.136 −7258.2 0 0 −7.3037 4.1653 × 10−6 2 273.2 < T < 647.1
DME 33.191 −3525.6 0 0 −3.4444 5.4574 × 10−17 6 131.7 < T < 400.1

Table 2
Wilson binary interaction parameters for DME–methanol–water system.

DME Methanol Water

ai,j bi,j ai,j bi,j ai,j bi,j

DME 0 0 −1.617 640.759 −2.2595 281.331

Methanol 7.90976 −3065.95 0 0 5.8335 −2057.172
Water −3.58498 −1629.76 −3.365 783.498 0 0

Fig. 3. Regressed vs. experimental data for vapor–liquid equilibrium of DME–methanol–water system.

T k = 2,. . .,NT. The feed flowrate, vapor flow duration and rate, and the
Tr =
Tc
3.3.2. Preliminary analysis
In order to get preliminary information regarding the sensitiv-
ity of DME production by catalytic cyclic distillation with respect
to operating parameters, a column with 15 stages (4 rectifying, 7
reactive, 10 kgcat /stage and 4 stripping) was chosen as base case.
The vapor flow rate along the column was considered constant,
Vk = V, k = 2,. . .,NT. Figs. 4 and 5 present simulation results, obtained
by solving the model equations described in Section 3.1, where the
vapor flow rate along the column was considered constant, Vk = V,
(40)
reflux were set to F = 0.15 kmol/cycle, tvap = 1 min, V = 1.5 kmol/min
and L = 1.425 kmol/cycle, respectively. The solution algorithm was
also well described at the end of Section 3.1. The values of the oper-
ating parameters and the results are in line with previous studies
on DME production by catalytic distillation [49,50] where typical
methanol conversions of about 0.5 where obtained using 24 reac-
tive stages with 10 kgcat /stage. Note that these studies considered
a macroporous sulfonic acid ion exchange resin as catalyst, which
has a lower activity as compared to Amberlyst 35.
The column achieves a methanol conversion of XMeOH = 0.92,
while the purity of DME (distillate) and water (bottoms) products

Table 3
Enthalpy of vaporization coefficients for methanol, water and DME.

C1 C2 C3 C4 C5 Range of validity Tc

DME 29,940 0.35050 0 0 0 131.7 < T < 400.1 400.1

Methanol 50,451 0.33594 0 0 0 175.5 < T < 512.5 512.5
Water 51,546 0.28402 −0.15843 0.2375 0 173.2 < T < 547.1 547.1
6 C. Pătruţ et al. / Chemical Engineering and Processing 81 (2014) 1–12
Fig. 4. Dynamics of composition on selected stages during several cycles.
slightly exceeds 0.9. The dynamic behavior of the column can be
presented from two different viewpoints. The Eulerian perspective
focuses on specific locations in space (the trays, k) through which
the fluid flows. The change of selected properties (mole fraction, x)
as time (t) passes is described. The evolution of the mole fraction
of DME in condenser, mole fraction of methanol on a rectifying
stage and mole fraction of water in the reboiler as time passes are
presented in Fig. 4.
Fig. 4 shows that a periodic state is established. In the condenser,
the concentration of DME first increases as the vapor coming from
the tray below is initially richer in the light component, then, at
the end of the cycle, drops to the initial value. On stage 3 (rectifying
zone), the concentration of the heavy component in the liquid phase
continuously increases during the vapor-flow period, then drops to
the initial value when liquid is brought from the tray above during
the liquid-flow period. The same behavior can be observed in the
reboiler. Here, the highest concentration of the heavy component
is attained at the end of the vapor-flow period. Therefore, this is
the right moment to withdraw the bottoms product, before liquid
is brought from the tray above.
Fig. 5. The changes in composition and temperature of the liquid moving through
time and space (Base case).
The Lagrangian perspective follows individual parcels of liquid
as they move through time and space (Fig. 5). The properties of
interest (mole fractions x, temperature T) are described in terms of
time. Because the residence time of the liquid on a stage is known, a
location on a certain stage can be assigned to each value of the time
variable. Fig. 5 shows that, along the reactive zone, the change of
the liquid phase composition is small. Therefore, the composition
on the last reactive stage could be used to calculate a conserva-
tive value for the reaction rate (this observation will be later used
for design). The discontinuities that occur on the feed stage and in
reboiler due to mixing can be also observed.
Figs. 6 and 7 present the distillate purity and the methanol
conversion, respectively, versus the vapor flow-rate, for dif-
ferent specifications of the distillate amount. The maximum
conversion is obtained when the distillate and bottoms prod-
ucts are removed from the column in almost equal quantities,
D = B = 0.075 kmol/cycle. Because the volatility of DME is very high
compared to the other species, all DME that is formed in the reaction
must be removed from the column with the distillate, the amount of
distillate setting an upper limit on the methanol conversion. There-
fore, a small amount of distillate leads to high purity DME and low
methanol conversion. On the other hand, the reactant will leave
the column with the distillate if this is increased, leading to low
conversion and low DME purity.
Fig. 8 presents the distillate purity and the conversion versus
the vapor flow rate, for different fixed values of the reflux amount.
For a given reflux, the range of vapor flow-rate values for which
a solution exists is limited. The upper boundary, represented by a
square in Fig. 8, corresponds to the second inequality in Eq. (19)
which signifies that the bottoms product must be removed from
the column in a positive amount. The lower boundary (triangle in
Fig. 8) occurs due to the requirement that the entire amount of DME
Fig. 6. Distillate composition versus the vapor flow-rate, for constant values of the
distillate amount (F = 0.15 kmol/cycle, D + B = F).
 C. Pătruţ et al. / Chemical Engineering and Processing 81 (2014) 1–12 7

Fig. 7. Reactant conversion versus the vapor flow-rate, for constant values of the distillate amount (F = 0.15 kmol/cycle, D + B = F).

formed in the reaction must leave the column with the distillate due - reflux:
to its much higher volatility. This condition can be written as:
L = V · tvap − D = 1.4325 kmol/cycle (43)
1
D = V · tvap − L≥ · F · XMeOH (41) - bottoms amount:
2
For any reflux amount, high purity distillate can be obtained B = F − D = 0.0825 kmol/cycle (44)
if the right vapor flow-rate is chosen, even if the conversion that
- composition of the bottoms product:
is achieved inside the column is not very high. In this case, the
unreacted methanol will leave the column through the bottoms 1 F · XMeOH
xB,W = · = 0.818 (45)
stream. 2 B

3.3.3. Design of catalytic cyclic distillation columns
Based on the feed amount, conversion, distillate or bottoms
purity, length of the vapor-flow period and the vapor flow-rate,
the design algorithm aims to find the number of stages in each
region of the column and the amount of products obtained. The
method will be explained on a specific case, the design of a column
which processes 0.15 kmol/cycle methanol. A methanol conver-
sion of XMeOH = 0.9 must be achieved. The vapor-flow period length
was set to tvap = 1 min and the vapor flow-rate to V = 1.5 kmol/min.
Two cases will be considered: high purity distillate, xD,DME = 0.995
(Design A) and high purity bottoms, xB,W = 0.995 (Design B), respec-
tively. In both cases, an additional distillation column is necessary
to recover the un-reacted methanol and to purify the product,
respectively.
The design starts by the preliminary mass balance of the col-
umn. The calculations will be exemplified for Design A (high-purity
DME):
F · (1 − XMeOH )
xB,MeOH = = 0.182 (46)
B
The algorithm used to determine the number of stages in strip-
ping section is based on writing the vapor flow equations from the
Lagrangian point of view. Assuming constant vapor flow along the
column, Eq. (2) can be recast in the following form, describing the
change of composition in the liquid phase as the liquid moves down
the column:
dxj (t)
M = V (yj (t + tvap ) − yj (t)) (47)
dt
where M = L + F is the tray holdup in the stripping section.
We note that, at a given time t, Eq. (47) contains the concen-
tration of the vapor coming from the tray below, tray which will
be reached by the liquid at a later time, t + tvap (due to periodicity
condition). The prediction implied by yj (t + tvap ) can be avoided by
reversing the sign of time in Eq. (47) through the change of variable
[36]:

- distillate amount (neglecting the impurities):  = NT · tvap − t (48)

1 This can be visualized as playing the movie of the parcel evolu-
D= · F · XMeOH = 0.0675 kmol/cycle (42)
2 tion backwards in time, therefore following the fluid from reboiler

Fig. 8. Distillate composition and reactant conversion versus the vapor flow rate, for constant values of the reflux amount.
8 C. Pătruţ et al. / Chemical Engineering and Processing 81 (2014) 1–12

Fig. 9. Design algorithm result for the stripping section. Left – Design A; right – Design B.

( = 0) moving upwards along the column ( > 0). In this formula- For comparison, we evaluated the performance of a classic cat-
tion, the vapor experienced by the liquid is in equilibrium with alytic distillation column, with the same number of trays as Design
the composition of the liquid at an earlier moment,  − tvap . The B and operated at the same vapour flow rate, V = 1.5 kmol/min. For
following equations can be written: a distillate rate D = 0.0825 kmol/min, the DME conversion achieved
is XDME = 0.86, while the purity of the bottom stream is only
dx() V
Reboiler : =− (x() − y()), 0 ≤  < tvap xWater = 0.9565. The bottoms purity can be increased to 0.994 by
d HB + B + V · 
increasing the distillate rate to 0.0925 kmol/min, but the conver-
(49)
sion drops to XDME = 0.698. When high performance is required, the
better performance of the cyclic system is obvious. Note that more
Transition from reboiler to tray NT − 1: information about the process performance of other reactive distil-
lation systems for DME synthesis is available in the open literature
x(tvap,+ ) · (L + F) + HB · xB = (HB + B + V · tvap ) · x(tvap,− ) (50)
[48–50].
dx() V
Trays : =− (y( − tvap ) − y()) (51)
d L+F 3.3.5. Stability and state multiplicity
The composition in the reboiler at the end of the vapor-flow The dynamics of the two catalytic cyclic distillation columns
period, xB,W , xB,MeOH , needed as initial condition, is provided by the was checked by simulating the dynamic behavior over several
preliminary mass balance. cycles. For Design A, very small, non-persistent disturbances in
The solution of the delay differential Eqs. (49)–(51) gives the the vapor flow rate and reflux amount (±0.001 kmol/cycle for 3
evolution of liquid phase composition using the reverse time  as cycles) resulted in the column drifting away from the operating
independent variable (Fig. 9). It can be observed that, after a certain point (Fig. 11). This leads to the conclusion that the periodic state is
period, no change of the liquid composition occurs. As the liquid unstable. Thus, obtaining high purity DME as distillate is not achiev-
stays on each tray for tvap , the number of stripping stages is easily able in practice when the column is operated at fixed vapor-flow
obtained (6 stages for Design A, 7 stages for Design B). rate and reflux amount. However, the system could be stabilized
To find the number of reactive stages, we recall the observation by feedback control of top and bottom composition, using reflux
(Fig. 5) that the change of the liquid composition in the reactive amount and vapor flow rate as manipulated variables.
zone is small, and a conservative estimation is given by the compo- Fig. 12 shows the dynamic behavior of Design B for much
sition of the top stripping stage. This allows calculating an average larger vapor flow rate and reflux disturbances (±0.02 kmol/cycle
value for the reaction rate, rMeOH,av , and finding the necessary for 10 cycles). In contrast to the previous case, the column returns
amount of catalyst which is further divided on trays:
F · XMeOH Table 4
mcat = (52) Design problem and the results obtained using the proposed design algorithm.
rMeOH,av
CCD Design A CCD Design B
Finally, the number of rectifying stages is determined by trial
(pure DME) (pure water)
and error. Basically, as many stages as required are added to achieve
the specified purity. Column design
Rectifying stages 3 3
Reactive stages 8 7
3.3.4. Rigorous process simulation Stripping stages 6 7
As a final point, the design is checked by solving the full model Feed stage 7 7
described by Eqs. (1)–(21) using the algorithm described in Section Catalyst [kg/stage] 10 10
3.3.1. The assumption of constant vapor flow is removed (Eq. (4) is Operating conditions
included). The characteristics of the catalytic cyclic distillation col- Feed [kmol/cycle] 0.15 0.15
umn, obtained by applying the design procedure, are summarized Vapor flow-rate (reboiler) [kmol/min] 1.5 1.5
tvap [min] 1 1
in Table 4.
Reflux amount [kmol/cycle] 4.3106 3.9856
As it can be observed from Table 4, the design procedure was
successful. The conversion achieved is almost 0.9; the DME mole Column performance
Conversion 0.8950 0.8990
fraction in distillate (Design A) and the water mole fraction in the Distillate [kmol/cycle] 0.0675 0.0825
bottoms (Design B) are near the imposed values, even if the vapor xDME in distillate 0.9945 0.8170
flow-rate is considered variable. Fig. 10 shows the concentration Bottoms product [kmol/cycle] 0.0825 0.0675
and vapor flow rate profiles along the column, calculated with the xWater in bottoms 0.8092 0.9994
Stability Unstable Stable
rigorous model considering variable vapor flow-rate.
 C. Pătruţ et al. / Chemical Engineering and Processing 81 (2014) 1–12 9

Fig. 10. Mole fraction, temperature and vapor flow rate profiles along the column, variable vapor flow-rate (Design A – top; Design B – bottom).

to the initial periodic state once the disturbance is removed.
Therefore, the operating point is stable and obtaining high purity
water as bottoms and DME – methanol mixture as distillate is
feasible.
In order to elucidate the nonlinear behavior of the catalytic cyclic
distillation column, the dependence of the periodic state versus the
reflux amount was traced. The results presented in Fig. 13 show
the coexistence, for the same values of the vapor flow rate and
reflux, of two periodic states. Moreover, there is no periodic state
when the reflux L exceeds the critical value corresponding to the
turning points of the diagrams. On the stable solution branch (con-
tinuous line), the distillate amount and the conversion are high,

Fig. 11. Dynamic behavior of Design A for small disturbances in the vapor flow rate (top) and reflux (bottom).
10 C. Pătruţ et al. / Chemical Engineering and Processing 81 (2014) 1–12

Fig. 12. Stable steady state behavior on vapor-flow-rate and reflux disturbances (Design B).

with the result of high purity water product (bottoms) and impure
DME (distillate). On the unstable branch (dashed line in Fig. 13), the
conversion is lower and a lower amount of distillate is obtained. The
DME concentration in the distillate is high and the bottom product
contains both methanol and water. Similarly to Fig. 8, the solution
branch ends at the point (marked by a square) where condition (41)
is no longer fulfilled.
It should be observed that the best performance (high con-
version, high distillate and bottom purities) could be obtained if
the reflux rate is chosen such that the operating point is near the
turning point of the diagrams. We stress that this operation is unde-
sired, as small disturbances or uncertainty of the design parameter
may result on moving the system to the region where no periodic
state exists.

Fig. 13. Steady state multiplicity of the DME cyclic distillation column (Design A).
 C. Pătruţ et al. / Chemical Engineering and Processing 81 (2014) 1–12 11

4. Conclusions Greek letters

˛ relative volatility
This study describes for the first time the catalytic cyclic distil-  activity coefficient
lation – a novel process intensification approach combining cyclic  heat of vaporization (J/kmol)
operation and reactive distillation in the same unit. Based on a gen-  stoichiometric coefficient
eral chemical reaction, it was shown that using a cyclic distillation  reverse time (s)
column instead of a conventional RD, much higher purity can be ˚ nonlinear mapping
obtained with less vapor flow-rate and fewer stages. It was also
proved that the catalytic cyclic distillation columns are far more
flexible than conventional catalytic distillation columns, since a Superscripts
higher range of purities can be achieved in a cyclic column than (V) end of the vapor-flow period
in a conventional RD unit. (L) end of the liquid-flow period
The periodic state behavior of catalytic cyclic distillation
columns was further investigated using a more complex case study, Subscripts
the DME synthesis. In this particular case, the maximum conver- k stage number (1 – condenser, NT – reboiler)
sion and purity are obtained when equal quantities of distillate A, B, C light, middle and heavy hypothetical components
and bottoms products are removed from the column. Moreover, the MeOH methanol
range of control parameters for which a periodic state is reached is W water
bounded by the requirement of a positive amount of bottoms and DME dimethyl-ether
by the condition of a distillate amount which is large enough to F feed
remove from the column the entire quantity of DME that is formed D distillate
in the reaction. B bottoms
Based on the studied behavior, a design algorithm was proposed.
The response of the column to perturbations and a parametric sen-
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