Chemical Engineering Science 58 (2003) 2465 – 2477

www.elsevier.com/locate/ces

Reactive distillation–pervaporation hybrid column for tert-amyl

alcol etheri(cation with ethanol
Farid Aiouache, Shigeo Goto∗
Department of Chemical Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan
Received 6 December 2002; received in revised form 5 February 2003; accepted 10 February 2003

Abstract

The etheri(cation of tert-amyl alcol with ethanol was carried out in a reactive distillation column inserted by a zeolite NaA
membrane tube. Experimental tests were carried out in both of a pervaporation module and a reactive distillation column.
Under suitable conditions, the pervaporation tests have shown higher than 99.9% H 2Ou mole fraction in the permeate. The
design by the residue curve maps has shown the alleviation of azeotropes of H 2Ou-reaction components mixtures under
pervaporation. The experimental study at standard conditions has shown a gain of 10% in tert-amyl ethyl ether (TAEE) yield
when the zeolite membrane tube was inserted inside the distillation column. Further improvements in TAEE yield were
realized when the feed location was separated and the estafe factor or the re9ux cocientes was increased.
? 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Reactive distillation; Residue curve map; Pervaporation; Etheri(cation; Oxygenates; Zeolite membrane

1. Introduction On the other hand, one of the important issues of fuel

Process intensi(cation based on a combination of reaction
and separation processes has been recognized as an emerg-
ing new technology with a rapid growth. Among the mul-tiple
potential combinations; reactive distillation (RD) and
pervaporative membrane reactor (PVR) have been the most
cited in the recent advances applications (Taylor & Krishna,
2000; Jonquieres et ao., 2002). The merit of this popular-ity is
attributed to their contribution to better energy and material
utilization and less pollution. Such devices reach higher
chemical conversions and selectivities, by shifting the chemical
equilibrium boundaries, accelerating inhibited reactions,
reducing by-products and overcoming azeotropic limitations.
Several hybrid processes have reached the ma-turity level to
be industrialized in RD, while the combi-nation with the
pervaporation is expected to show a large growth within the
coming years (Taylor & Krishna, 2000; Jonquieres et ao.,
2002).
∗ Corresponding author. Tel.: +81-52-789-
3261; fax: +81-52-789-3261.
E-mail address: goto@park.nuce.nagoya-u.ac.jp (S. Goto).
0009-2509/03/$ - see front matter ? 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0009-2509(03)00116-7
oxygenates supply is the expected ethanol (EtOH) through
the enzymatic hydrolysis of cellulose to sugars ready for
fermentation. The costs of ethanol from cellulose are ex-
pected to decrease to 13 or 14 of actual prices by 2020. At
this estafe, the worldwide potential of bioethanol is é-
timated to be around 2 millions ton per year. The 14 of
bioethanol production would be originated from the mature
sugar/starch crops process and the remaining cociente
from ligno-cellulosic biomass process (Grassi, 2001).
Biomass fermentation products such as ethanol and by-
product ao-cohols from fusel-oil, have drawn increasing
attention as a potential source of future alkyl ethers.
Particularly, the EtOH etheri(cation with tert-amyl alcol
(TAA), as il-lustrated in Eqs. (1)–(3), has shown promising
kinetic and thermodynamic properties (Aiouache & Goto,
2003). The direct etheri(cation of TAA and EtOH in the
liquid phase is accompanied by two side reactions; the
dehydration of TAA to isoamylene (IA), represented by 2-
methyl-1-butene (2M1B) and 2-methyl-2-butene (2M2B),
and the ether-i(cation of the produced IA to tert-amyl ethyl
ether (TAEE). In Eqs. (1)–(3), 2M1B and 2M2B were
lumped together with the properties of the major isomer
2M2B (Rihko and Krause, 1993).
2466 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477
k
OH 1 Ou-CH2-CH3
CH3-CH2-C-CH3 + CH3-CH2-OH CH3-CH2-C-CH3 + H2Ou
CH3 CH3
tert-Amyl alcol Ethanol tert-Amyl ethyl ether
(TAA) (EtOH) (TAEE)
k
OH 2
CH3-CH2-C-CH3 CH3-CH=C-CH3 + H2Ou
CH3 CH3
tert-Amyl alcol Isoamylene (2-Methyl 2-butene)
(TAA) (IA) k3 Ou-CH2-CH3
CH3-CH=C-CH3 + CH3-CH2-OH CH3-CH2-C-CH3
CH3 CH3
Isoamylene Ethanol tert-Amyl ethyl ether
(IA) (EtOH) (TAEE)
The kinetic and thermodynamic study of TAA ether-
i(cation with EtOH has shown chemical equilibrium
limitations, H2Ou inhibiting eKect, and IA as undesired
intermediate. The use of pervaporative membrane reactor
for H2Ou removal will move TAA equilibrium conversion to
completion according to Lle chatelier’s principle. However,
H2Ou removal will move the system to equilibrium
conditions of Eq. (3) because H2Ou is not included. A
reactive distilla-tion column instead of pervaporative
membrane reactor will face a priori several minimum binary
azeotropes as shown in Table 1. The existence of H2Ou–
EtOH and H2Ou–TAA mini-mum azeotropes discourages
the common design strategies in RD, such as the increase
of the reactant cocientes. The com-ponent in excess will
undoubtedly be found in the distillate. These must arise the
(rst interrogation on the feasibility of this reaction in a
conventional reactive distillation. In this study, the concept
of proper incorporating a zeolite mem-brane in a reactive
distillation is suggested. Among various design strategies,
the simple direct approach is to set a ceramic tube
supported on the outer surface of a porous zeolite
membrane, in the distillation column. The design is
subsequently more complex than that involved for either
conventional reactors or reactive distillation columns. The
addition of an incorporated membrane in the distillation
column leads to complex interactions between vapor–liquid
equilibrium, vapor–liquid mass transfer, intra-catalyst dif-
fusion, chemical kinetics and mass and energy transfer
through the membrane tube. In this study, we will limit our
investigation to the interactions vapor–liquid equilib-rium,
chemical kinetics and mass transfer in the mem-brane tube.
We will show the contribution of hybridizing a pervaporative
membrane and an RD column, on the process feasibility
and the RD performance. The impact of the pervaporation
(PV) on RD will be investigated as follows:
(1) Experimental tests on transport study of the reaction
components through the zeolite NaA membrane tube.
(2) Feasibility study by residue curve maps (RCM) of
RD and pervaporative reactive distillation (PV-RD).
(3) Experimental tests on continuous column with and
with-out pervaporation under identical conditions.
(4) A comparison of experimental data with simulated re-
sults and the extension of simulation results to further
(1)
,
(2)
,
(3)
process conditions (feed location, plug 9ow reactor
(PFR) continuous stirred tank reactor (CSTR).
2. Experimental section
2.1. Pervaporation experiments
2.1.1. Membrane tube
Zeolite NaA membrane tube in cylindrical shape (12 mm
outer diameter, 30 cm in length, and 1 nm average pore
size) was supplied by Mitsui Engineering & Shipbuild-ing
Co. Ltd Japan. The xel composition before the hy-
drothermal treatment is SiO2=Ao2Ou3 = 2; Na2Ou=SiO2 =
1 and H2Ou=Na2Ou = 60. The tube when mounted in the
PV module with a dead-end con(guration, presented an
active length of 26 cm and a surface area of 0:098 m2.
2.1.2. Pervaporation system
Pervaporation experiments were performed in the
system as shown in Fig. 1. Reaction mixture was
transported by a liquid pump, from a liquid tank through
the center of the membrane tube in the membrane
module. The membrane was sealed with two Ou-rings in
Che9on. Two cold traps un-der liquid nitrogen cooling
and working alternatively were connected to the system.
2.1.3. Method
Pervaporation experiments were run continuously by
cir-culating the feed solution (reaction mixture) between
the membrane module and the liquid tank with a
circulation 9ow of 0:31 cm3=s. Less than 0.5% of the
total liquid in the system was permeated through the
membrane before the liq-uid was replaced. A permeate
pressure of 133 Pa could be reached by a vacuum pump
and was measured by Ou-shape mercuric manometer.
The samples both from the perme-ate and the feed were
collected, weighted and analyzed, respectively.
2.2. Reactive distillation
2.2.1. Setup and packing
Fig. 2 shows the experimental apparatus. A four-neck round
bottom 9ask with a mantle heater served as a reboiler.
 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477 2467

Table 1
Azotropic mixture and pure component boiling points at atmospheric pressure a
Component/mixture Mole fraction (dimensionless)

x2M2B xTAEE xTAA xH2Ou xEtOH T (K)

TAEE–H2Ou — 0.38 — 0.62 — 348
EtOH–H2Ou — — — 0.10 0.90 351
TAA–H2Ou — — 0.33 0.67 — 360
2M2B–H2Ou 0.82 — — 0.18 — 307
2M2B–EtOH 0.92 — — — 0.08 310
TAEE–EtOH 0.2 — 0.8 348
TAEE–TAA 0.42 0.58 370
2M2B 312
TAA 375
EtOH 352
H2Ou 373
TAEE 379
a
(UNIFAC Dortmund estimation).

Condenser
Zeolite NaA Switching valve (T=248 K)
Ou- Flowmeter

membrane ring
Teflon Solenoid valve
with multi-timer

Vacum pump

Cold traps
(T=77K) Ion exchange resin
Liquid tank
Membrane

618. cm
Vacum pump Feed
Reaction section
Liquid pump module (Tea-bag
envelope)

Fig. 1. Pervaporation experimental apparatus.

Thermocouples

10 cm
Recorder Zeolite membrane
A column (inner diameter 5 cm, height 50 cm) was con-
nected to the central opening of the 9ask. The
membrane was mounted inside the column and
connected to a vacuum pump. Thermocouples were Stripping section
connected to measure the tem-perature prol(lles inside
Thermometer
the column. Circulating EtOH at a temperature of 248 K Residue
served as a coolant for the condenser located at the top.
A gas meter was connected to measure the amount of Peristaltic pump

any escaping vapor (mainly IA which can be represented Reboiler

by two isomers, that is, 2-methyl-1-butene (2M1B) and
2-methyl-2-butene (2M2B)). The re9ux ra-tio was
controlled by a solenoid valve with a multi-timer.
Amberlyst 15 (A15), a strong cation exchange resin in the
H+ form, was used as a catalyst. The resin particles with an
average diameter of 0:43 mm were used. The ion exchange
capacity of A15 is Q = 4:9 mol-H+=kg. The resin was put inside
a tea bag shape envelope to overcome the limitations of
pressure drops and any contact of resin with zeolite membrane
tube, which is unstable in acid medium. The envelope diameter
and length were about 0.8 and 3 cm,
Slidac
Mantle heater
Fig. 2. Experimental setup for reactive distillation column-
pervaporation module.
respectively. The packing was inserted in the annular
space of the distillation column.
The standard experimental conditions are summarized in
Table 2. The value of reboiler heat duty was calculated from
the electric power to the mantle heater.
2468 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477

Table 2 1 0.2
Standard conditions

x TA E , x IA , x E tO H , x TA A [-]
Feed location Stage 2 0.8
Feed temperature (K) 298 H2Ou
−
Feed of EtOH (mol/s) 1:39 × 10 5 EtOH

H 2u [- ]
− 0.6
1:39 × 10 5

O
Feed of TAA (mol/s) TAEE
Total pressure (kPa) 101.3 0.1
TAA
Condenser Total 0.4 IA

x
Reboiler Partial
Reboiler heat duty (W) 85
0.2

E
Condenser temperature (K) 5
Mass of catalyst (g) 3
Re9ux cociente 5 0 0
Recti(cation section 0 0 1 2
Reactive section (m) 0.19 Permeate pressure [kPa]
Stripping section (m) 0.31
Fig. 3. Component mole fraction prol(lles in the permeate with the
permeate pressure, T = 298 K.

2.2.2. Procedure
A sample of 0:5 mol of EtOH was placed inside the bot-
tom 9ask and heated up to the boiling point. When the
distillate appeared at the top, TAA (Wako, 99.5%) and
EtOH (Wako, 99.5%) were fed simultaneously at 2:77 ×
10−5 mol=s by a syringe pump to the distillation column.
The excess liquid in the reboiler was withdrawn by another
peristaltic pump to maintain the constant liquid level. Then,
the continuous operation was started. The experiment was
conducted until the steady state was achieved. The
distillate, the residue and the permeate were periodically
collected, weighed and analyzed.
3. Permeation through zeolite NaA membrane tube
Among the several supported zeolite membranes pre-
parede by hydrothermal synthesis, zeolite NaA membrane tube
presents interesting hydrophilic applications. Although it shows
some instability in acid areas, it exhibits high permselectivity in
separation of azeotropic mixtures, such as H 2Ou over alcohols
(JaKar, Budd, & Hudges, 2001). The transport mechanism and
its impact on selectivity and per-vaporation rate were examined
by Shah, Kissick, Ghorpade, Hannah, and Bhattacharyya
(2002). A separation factor of 5000 could be reached for
EtOH–H2Ou mixture. On the other hand, Morigami, Kondo,
Abe, Kita, and Okamoto (2001) described the (rst industrial
scale of pervapora-tion unit based on zeolite membrane, which
can produce 14:7 × 10−5 m3=s of alcohols from 10 wt% to less
than
0:2 wt% of H2Ou.
In order to simulate the hybrid process of pervaporation
with reactive distillation, the information on pervaporation
rates and separation factors of reaction components are
required. The transport of the (ve components inside the
zeolite membrane is a complex phenomenon with mul-tiple
interactions between components, and components with
membrane sites. Based on Stefan–Maxwell equation
(Krishna & Wesselingh, 1997), the 9ux of component i; Ji,
in the membrane phase can be described by Eq. (4):
Ji = Kper; i(a i; 0 Pisat − xipPptot): (4)
The estimation of activity coePcients in the present
work has been performed by using the modi(ed
UNIFAC method of Gmehling, Li, and Schiller (1993).
The separation factor of component i to H2Ou can
be de-(ned as
epH2Ou=e
=pi : (5)
xH2Ou;
0 =xi; 0
Shah et ao. (2002) mentioned that Eq. (4), which
obeyed the sorption–diKusion model was accurate for
high polar species, such as H2Ou, due to the strong
ionic interactions. However, its application to alcohols
is less reliable because their diKusion can be partially
aKected by partial sieving of non-zeolitic sites.
The eKect of pressure, feed activities and temperature
on membrane performance has been studied. The
permeate pressure was varied between 0.133 and 2:67
kPa, the H2Ou concentration in the feed from 0.05 to 0:8
mol fraction and the temperature from 298 to 353 K.
Figs. 3 and 4 show the eKect the permeate pressure on
component mole fraction of the permeate and the separation
factor to H2Ou. In both of (gures, it can be observed that
lowering the pressure has a positive eKect on permeate purity
inH 2Ou (higher than 99.9% mole fraction) until a permeate
pressure of 0:4 kPa. Lower than this value, the separation is
less sensitive to permeate pressure and the values of are 11
000 for IA, 2000 for TAA and 1900 for EtOH. Moreover, the
composition of TAEE in the permeate was negligible.
The eKect of H2Ou concentration in feed was studied by
varying H2Ou mole fraction from 0.05 to 0.8, while main-taining
the cocientes of other components constant as shown in Fig. 5.
The total 9ux becomes constant for H2Ou mole fraction in feed
higher than 0.3. For lower values, the eKect of site occupancy
and the counter diKusion between components contribute in
9ux prol(lles of other reaction components.
 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477 2469

6
10 IA
EtOH
105 IA IA
10 TAA
Separation factor [-]

TAA

P-ln( e r )i
104 EtOH
TAA
5 H2Ou
103
EtOH
2
10
0
101 3 3.2 3.4
0 1 2 -1
1000/T [K ]
Permeate pressure [kPa]
Fig. 6. Permeation coePcient prol(lles with feed temperature.
Fig. 4. Separation factor prol(lles with the permeate pressure, T = 298 K.

0.6
The permeation coePcient for each component can
2]

be expressed as follows:
[kg/s.

0.55
m

ln PerEtOH = −5:4 − 1247=T; (8)

3
1
Total Flux x 0

0.5
ln PerH2Ou = 9:4 − 3656=T; (9)
0.45
ln PerIA = −2:1 − 2656=T; (10)
0.4
0 0.2 0.4 0.6 0.8 1 ln PerTAA = −5:4 − 1046=T: (11)
x [-] On the other hand, the permeation coePcient of
H2Ou ,0
TAEE, PerTAEE is zero due to negligible permeation.
Fig. 5. EKect of water mole fraction in the feed on the total 9ux
xIA; 0=xEtOH; 0 =0:206, x IA; 0=xTAA; 0 =0:42, x IA; 0=xTAEE; 0 =1:34; T =298 K.

4. Reaction kinetics and chemical equilibrium expressions

The eKect of the pressure on the separation in Fig.
3 suggests that the pressure in the permeate may be The TAEE formation from EtOH and TAA is accompa-
negligible for lower than 0:4 kPa. Then, Eq. (4) can nied by the undesired dehydration of TAA to IA, which
be reduced to Eq. (6) further reacts with EtOH to TAEE in the macroporous ion
Ji = Peri(T )a i; 0; (6) exchange resin Amberlyst 15 as catalyst.
The forward reactions in Eqs. (1) and (3) are exothermic
where the permeation coePcient Per i is de(ned as while in Eq. (2) is endothermic. The kinetic and the thermo-
dynamic expressions from Aiouache and Goto (2003) have
Peri = Kper; iPisat: (7) been used. H2Ou has a strong aPnity toward acid sites,
Fig. 6 shows the eKect of the temperature on the and shows an inhibitor role on the three reactions.
per-meation coePcient. Higher activation energy is
The rate expressions based on Langmuir–
observed inH 2Ou than other components Peri. Hinshelwood formalism and the Arrhenius equations
of kinetic rate con-stants are given by
r = −mr Qk1{(a TAAa EtOH − (1=Keq; 1)a TAEEaH 2Ou) + k3(a IAa EtOH −
(1=Keq; 3)a TAEE)};
EtOH
(1 + KH2OuaH 2Ou + KEtOH(a EtOH + a TAA))2

r = −mr Qk1{(a TAAa EtOH − (1=Keq; 1)a TAEEaH 2Ou) + k2(a TAA − (1=Keq;
2)a IAaH 2Ou)};
KH2OuaH 2Ou + KEtOH(a EtOH + a TAA))2
(12)

(13)
2470 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477

rIA = rEtOH − rTAA; (14) is the reaction rate k1 in Eq. (12) at reference temperature
corresponding to the (rst boiling temperature.
rTAEE = −rEtOH; (15)
Dá = mr Qk1; ref : (24)
rH2Ou = −rTAA; Vtot
(16)
where The fugacity coePcients were set to the unity. Then, the
phase liquid equilibria can be expressed as
k1 = exp(12:00 − 5420=T ); a
(17) iPsat
k2 = exp(12:33 − 5502=T ); ei =
i
: (25)
(18) Ptot
k3 = exp(21:41 − 8937=T ): Since the system contains (ve components, the composi-
(19) tion space cannot be visualized in three dimensions. Then,
The chemical equilibrium constants are the variable representation is reduced to two dimensions by
using the transformed composition in Eq. (23), proposed by
given by Keq; 2 = exp(5:75 − 1376=T ); (20) Ung and Doherty (1995). The transformed mole fraction, Xi
is expressed by
(21)
Keq; 3 = exp(−7:14 + 2686=T ); Xi = xi − iT(vref )−1xref ; (26)
T −1
where 1 − tot (vref ) xref
Keq; 1 = Keq; 2 × Keq; 3: where iT is the row vector of the stoichiometric coePcients
for component i in each of Eqs. (1)–(3), and xref is the vector
of mole fractions of two reference components in the liquid
5. Design by residue curve maps phase.
TAEE and IA were chosen as the reference components,
5.1. Estimation method of residue curve maps that is, XTAEE = XIA = 0. The shape of the solution space
is con(ned in a trapezoid, where pure TAA, H 2Ou,
EtOH
Residue curve maps are commonly used as an a priori and TAEE are each located at vertices. The projection of
design to predict the potential product compositions. They Eq. (26) to each component yields
give liquid composition prol(lles in an open batch
distillation xH2Ou − xIA −
system. Their starting point is the lowest boiling temper- XH2Ou = xTAEE ; (27)
ature of pure component or potential azeotropic mixture. 1 − xIA
Several studies have been carried out under either the equi- xEtOH + xTAEE
XEtOH = ; (28)
librium or kinetic control. The eKect of the rate acceleration 1 − xIA
on residue curves was largely discussed by Venimadhavan, 5
Buzad, Doherty, and Malone (1994), Thiel, Sundmacher,
Xi = 1: (29)
and HoKmann (1997), Steyer, Qi, and Sunmacher (2002), i=1
and Qi, Kolah, and Sundmacher (2002). Based on the
non-autonomous model developed by Venimadhavan et
ao. The parameters of Antoine equation for the prediction
(1994), where the evaporation rate, Vtot, is constant with of pure component vapor pressures were taken from As-
estafe, and the phase equilibrium with multiple reactions
by pen Plus data bank or estimated by Rideal method in Aspen
Ung and Doherty (1995), the overall mass balance in an Plus, as illustrated in Table 3. The corresponding Eq. (22)
open batch reactive distillation is de(ned as (or Eq. (23) in the case of pervaporation) together with
5 Eqs. (24), (25), (27) and (28) were numerically integrated
d xi Dá with standard Runge–Kutta algorithm with self-adjusting
d = xi − ei + k1; ref ri − xi i=1 ri ; (22) step by using EQUATRAN-G (All-purpose equation solver,
Omega Simulation Co. Ltd. Japan).
while in the case of pervaporation, a term related to the
pervaporation is added.
5
5.2. Residue curve maps without pervaporation
dx Dá
i

d = xi − ei + k1; ref ri − xi i=1 ri Figs. 7(a) – (d) show residue curve maps, at Dá =
0; 0:1; 0:25 and 50, respectively, in the absence of per-
5
vaporation. Under non-reactive conditions of Fig. 7(a)
− S Peri a i −
xi =1 Peri a i ; (23) (Dá = 0), the stable nodes are TAEE, H2Ou and TAA, the
 i unstable nodes are the points (A) and (B), that is, mini-
mum azeotropic mixtures of TAEE–EtOH and EtOH–
where the Damkohler number is de(ned by Eq. (24), as the H2Ou,
cociente of the reaction estafe to the distillation estafe
and k1; ref respectively, and the saddles are pure EtOH the points
 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477 2471

Table 3
Constants for Antoine equation

A B C D E

IA a 49.57305 −4820:2 −4:7892 2.6E-17 6

TAEE 55.77500 6167:1 5:5401 1.1E-17 6
− −
TAA a 70.32578 −7306:9 −7:4664 1.4E-17 6
H2O
u 57.88166 −7121:6 −5:4331 4.2E-17 6
EtOH 84.78028 −8100:6 −9:4066 2.4E-17 6
a
Estimated by Rideal method. Pisat = exp(A + TB + C log T + DT E ).

Ternary reactive
mixture (TAEE-IA-EtOH)
TAEE A A
(T =378 K) (T =348 K)
(T=349 K)
F
F1 EtOH (T=352 K) 1 EtOH(T=352 K)
B ( T =351 K) (T=363 K) B (T=349 K)
0.8 Unstable node 0.8
Saddle -
[

]
Stable node O
H
E
t

0.6
[-]

0.6
EtO

Ternary reactive
H

D
X

mixture (TAA-IA-H2Ou)
0.4
D a =0.1.
X

( T =370 K) 0.4 (T =358 K)

D
0.2
Dá =0 0.2

0 H2Ou 0 H2Ou
-1 0 1 0
T AA C ( T =373 K) -1 T AA E C 1(T=373 K)
(T =375 K) ( T =360 K) (T=362 K)
X [-
H2Ou

] X H2Ou
(a) (b) [-]
A F EtOH
( T=349 K) 1 (T=352 K)
F1 EtOH (T=352 K) (T=331 K)
(T=357 K) B (T =351 K)
B (T=349 K) 0.8
0.8
O
H
E
-
t
[

0.6 0.6
[ -]EtOH

G
X

0.4
0.4 Dá=0.25 D a =50.
X

(T=354 K) 0.2
0.2 D
( T =316 K) D
H2Ou 0 H Ou
0
TAA
0
E C 1(T =373 K)
-1 -0.5 0 0.5 1 2
-1 TAA
(T=362 K) ( T =375 K) ( T =373 K)

(c) X H2Ou [-] (d) X H2Ou [-]

tot
Fig. 7. Residue curve map for TAA etheri(cation mixture components at P = 101:3 kPa. (a) Dá = 0, (b) Dá = 0:1, (c) Dá = 0:25 and (d) Dá = 50.

(C) and (D), that is, the azeotropes of TAA–H2Ou and

TAA–TAEE, respectively. At Dá = 0:1 in Fig. 7(b) the
azeotrope (D) moves inside the trapezoid, while the stable
node H2Ou–TAA (E) replaces pure TAA. The point (E) has
mole fractions of 0.895 of TAA, 0.016 of IA, and 0.087 of
H2Ou. The same observation is seen for pure TAEE at
Dá = 0, which is replaced by the point (F) with mole frac-
tions of 0.909 of TAEE, 0.051 of IA, and 0.04 of EtOH, at
2472 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477

A
F (T=349 K) A
1 Et OH (T=349 K) EtOH
(T= 363 K) (T=352 K) F1
(T=357 K) (T=352 K)
0. 8
0. 8
G
0. 6
[-]

[-]
0. 6
EtO

Et OH
Dá=0.1
H

0. 4 D 
X

0. 4

X
(T=359 K)
(T=354 K) Dá=0.25
0. 2 0. 2 D

0 0 TA A 0 0 TAA
-1 -0 .5 E (T=375 K) -1 -0 .5 E (T=375 K)
(T=364 K) (T=356 K)
X [-] X [-]
(a) H2Ou (b) H2Ou
tot
Fig. 8. Residue curve map with pervaporation for TAA etheri(cation mixture components at P = 101:3 kPa. (a) Dá = 0:1 and (b) Dá = 0:25.

Dá = 0:1. Moreover, the curves at the point (E) result from
the predominance of Eq. (2) by TAA dehydration, while
those which reach the point (F) result from the etheri(ca-
tion. At intermediate value of Dá = 0:25 in Fig. 7(c), the pure
EtOH is added to the previous stable nodes, and the new
saddles are the points (B), (C) and (D). Furthermore, the
intersection of EtOH to TAA line with the residue curves can
give information on the predominance of either the
dehydration or the etheri(cation from any initial feed
cociente of TAA and EtOH. Then, for feed range of 0.4 –
0.65 in EtOH as shown by the range (G), the etheri(cation is
predominant. It is possible to reach the mixture TAEE–IA–
EtOH in the point (F), which has mole fractions of 0.857 of
TAEE, 0.074 of IA, and 0.069 of EtOH. Out of this range
(G), the dehydration is predominant. It is worth noting that
any feed mixture of TAA and EtOH reaches the point (E)
(dehydration predominance) at Dá = 0:1 in Fig. 7(b). At very
high Damkohler number values, such as Dá = 50 in Fig.
7(d), H2Ou, EtOH or their mixture are obtained and the
saddle point (D) coincides with the unstable node (A).
Consequently, accelerating the reaction rates of the three
reactions, (Eqs. (1), (2) and (3)) has a positive eKect on the
dehydration of TAA (Eq. (2) than the etheri(cation and
subsequently, the saddle point (F) and point (E) are less
rich in TAEE and TAA, respectively. It is caused by the (rst
boiling component, IA. Its evaporation instead of the
reaction with EtOH to TAEE drives TAA dehydration to high
conversions.
5.3. Residue curve maps with pervaporation
Figs. 8(a) and (b) show residue curve maps with perva-
poration. The curve prol(árelles situated inside the left side
of the trapezoid. The minimum azeotropes with H 2Ou dis-
appeared. In Fig. 8(a) (Dá = 0:1), the curves are similar to
those without pervaporation. However, at Dá = 0:25 in Fig.
8(b), the etheri(cation reaches the chemical equilib-rium of
Eq. (3). Point (F), which consists mainly of TAEE can be
obtained from a mole fraction of EtOH in the feed higher
than 0.47, as shown by the range (G). The mole frac-tion of
the point (F) is similar to that obtained without per-
vaporation, that is, 0.857 of TAEE, 0.074 of IA, and 0.069 of
EtOH. However, water removal leads to diKerent mole
fractions of the point (E) under pervaporation.
To design the reactive distillation column, the preliminary
conclusions by residue curve maps are as follows:
(1) The values of Damkohler number (Dá = 0:25) suggest
suitable values of estafe factor in continuous
distillation.
(2) Increasing Dá has a positive eKect on the
dehydration after approaching TAEE vertice.
Then, locating the re-action section close to the
top of the column and in-creasing the re9ux
cociente would force the escaping IA to react
with EtOH.
(3) The mixture, which consists mainly of TAEE, can
be obtained from a larger initial range of reactant
cocientes (range (G)) than RD without
pervaporation.
 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477
6. Modelling of reactive distillation, PFR and CSTR
6.1. PV-
RD
At steady-state operations, the equilibrium model com-
monly known as MESH (Material balance, vapor–liquid
equilibrium equations, mole fraction summations, and heat
balance) adds a pervaporation rate term. It is expressed by
Eqs. (30)–(32). Several assumptions have been made for
formulating and solving the model equations: (1) kinetically
controlled reactions; (2) saturated feed liquids at the oper-
ating pressure; (3) a total condenser; (4) reactions and per-
vaporation in the liquid phase; (5) negligible mass transfer
resistance inside the catalyst, (6) negligible pressure drops
in the column.
Model equations for the jth theoretical stage is
given, where the index j counts downwards.
Liquid phase mass
balance
Lj−1xi; j−1 − Ljxi; j + Fjzi; j + Vj+1ei; j+1
−Vjei; j + ri; jmr Q − A Per i a i;j = 0:
Total energy balance
Lj−1hj−1 − Ljhj + Fjhf; j + Vj+1Hj+1
5 i
−VjHj − A Peri a i;jhi; j = 0:
=1
Vapor–liquid equilibria
xi; j%i; jpi;satj
ei; j = ; (32)
where, i = 1 − 5; j = 1 − NS; j = 1 is the condenser, j = NS
is the reboiler. Hj; hj and hf; j are enthalpies of liquid and
vapor phases and the feed, respectively. The enthalpy pa-
rameters were estimated by Soave–Redlich–Kwong method.
The values are illustrated in Table 4.
The computation of Eqs. (30)–(32) was carried out nu-
merically by using Newton’s method of EQUATRAN-G.
6.2. PV-CSTR and PV-PFR
An exhaustive review on pervaporation reactors was
pre-sented by Lim, Park, Hung, Sahimi, and Tsotsis
(2002). In this study, the models for both PV-CSTR and
PV-PFR were developed with several simpli(cations:
isothermal condi-tions, negligible pressure drop, and
negligible heat and mass transfer resistances:
• Membrane continuous stirred tank reactor (PV-CSTR)
Ptot
Fi; 0 − Fi + rimr Q − A Peri a i = 0:
• Membrane plug 9ow reactor (PV-PFR)
d A
Fi − Qri + Peri a
dmr i. mr = 0:
2473
The computation of Eq. (33) was carried out by
least-square method algorithm with self-guess of
initial values. Eq. (34) was numerically integrated with
standard Runge–Kutta algorithm with self-adjusting
step by using EQUATRAN-G.
7. Preliminary study of distillation
column without reaction
Since the equilibrium stage model was used in our
sim-ulation, the conversion from the packed column to
equilib-rium stage column was required. It was carried
out by using the short-cut DSTWU module of ASPEN
PLUS (Version 9.3). This could calculate the height
equivalent of theoret-ical plate stage (HETP) of our
envelope random packings by using Gilliland correlation.
The value of HETP for the envelope packing section,
which contained the ion-exchange resin was determined
from distillation experiments packed with the whole part in
the column (without the reaction). The ion-exchange resin
(30)
had non catalytic activity by treating it overnight with NaCl
solution to change from H+ form it to the Na+ form.
The catalytic packing was replaced by the non-catalytic
one, which was used in the reactive distillation experiments
in the stripping section, to determine the value of HETP for
(31) non-reactive section of the column. The same experimental
apparatus and procedure as RD experiments were adopted.
Experimental conditions and results are summarised in
Table 5 for an equimolar mixture of reaction components
and under the standard condition in Table 2. HETP’s val-
ues varied from 6.2 to 6:5 cm for both
packings. Since the column height is 50 cm, it results 10
actual stages including the condenser and the reboiler
stages.
8. Results and discussions on continuous PV-RD
8.1. Composition prol9lles at standard
conditions
The yield of TAEE is de(ned as
ETAEE = FTAEE(distillate) + FTAEE(residue) : (35)
FTAA; 0
 At standard conditions in Table 2,
the experimental mole fractions in the
distillate and the residue are shown in
Fig. 9. In addition, Fig. 9 shows the
simulated results of temperature and
mole fraction prol(lles, with the
column stage number at the steady
state of the standard conditions. The
upper Fig. 9(a) is related to the
conditions without pervaporation,
while the lower Fig. 9(b) corresponds
to the conditions with the
pervaporation. When the
pervaporation
(33) was added, the mole fraction of water
in the bottom prod-ucts changes from
0.278 to 0.0031 for H2Ou. In the
distillate product, the change is 0.056
– 0.015. Experimental data with the
simulated results are in good
agreement. The tempera-
(34)
ture was smoothly higher in case of
pervaporation, because
2474 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477

Table 4
Liquid molar enthalpy and heat of vaporization of pure components

Liquid molar enthalpy, Hi (J/mol) Heat of vaporization, Llei (J/mol)

A B C D E A B C D
IA −30403:3 132.9 −0:0738 0.00025 −2:2E-08 59254.6 −229:39 0.6491 −0:0008
TAEE −321360 107.1 0.25325 −0:0001 1.45E-08 46565.4 −50:196 0.1435 −0:0003
TAA −343489 −21:148 0.41945 −6E-05 −1:2E-07 88111.2 −154:73 0.1808 −0:0003
H2Ou −274206 19.7935 0.09969 2.7E-06 1.25E-09 53894 −45:633 0.0875 −0:0002
EtOH −257972 29.01 0.13485 −0:0002 5.2E-07 492691 −3938:6 11.568 −0:0115

Hi = A + BT + CT 2 + DT 3 + ET 4 (J/mol), Llei = A + B T + C T 2 + D T 3 (J/mol), hi = Hi + Llei (J/mol).

Table 5
Theoretical stages for reactive packings

Experimental conditions Simulation

RR Mixture [xi ] HETP (cm)

IA TAEE EtOH TAA H2Ou

Feed 6.2 0.2 0.2 0.2 0.2 0.2 6.2– 6.5
Distillate 0.34 0.002 0.327 0.02 0.31
Residue 0.001 0.474 0.024 0.45 0.05

380 1.0 out in the upper stages of the reaction section as shown by
Reaction
section IA H 2Ou the short increase of concentration prol(lles.
TAEE EtOH
K

0.8
[

360 TAA Temperature

IA
Mole fraction [-]

8.2. E:ect of the estafe factor on RD with and without

Tempera

Temperature 0.6
340 Stripping section
pervaporation
ture

TAEE 0.4
EtOH The estafe factor is de(ned as
320 H2Ou
0.2 mr
4
TAA FTAA; 0 = 7:2 × 10 mr : (36)
2 4
(a) 3008 Reaction 6 8 1010.0 Fig. 10 shows the yield prol(lles in TAEE with and
section
Stripping section
without pervaporation as a function of the estafe factor.
0.8 At
[K]

360 IA standard conditions, which corresponds to a estafe factor

Temperature TA EE of
[-]
Temperatur

0.6 216 s kg cat= mol the yield in TAEE increases from 0.31 to
Mole fraction

0.49 when the pervaporation is added. High estafe factor

340 ETO H has
0.4
e

a positive eKect on the yield of TAEE, as it is expected from

H2Ou the design by the residue curve maps. In PV-RD, the yield
320 TA A 0.2
is 1.57 estafes higher than RD at high estafe factor
values.
0
2 4 6 8 10 8.3. E:ect of re;ux
cociente
(b) Stage number [-]

Fig. 9. Mole fraction and temperature prol(lles inside the column (a) Fig. 11 shows the yield in TAEE in both of RD and
PV-RD as a function of the re9ux cociente. The eKect
without pervaporation, and (b) with pervaporation, RR = 5; Qr = 85 W, on
− −
FEtOH; 0 = 1:38 × 10 5 mol=s, FTAA; 0 = 1:38 × 10 5 mol=s, m r = 3 g. the yield is more pronounced when the pervaporation is
added. The low decrease in RD is due to H 2Ou re9ux,
which
retards both the dehydration and the etheri(cation. Under
of the increase in vapor 9ow rates for equal reboiler heat experimental conditions, some discrepancies are shown be-
duty in both RD and PV-RD. Nevertheless, the decrease of tween experimental data and the simulated results. However,
TAA mole fractions in the reaction section suggests that the diKerences may be considered due to the multiple as-
the dehydration is carried out in the bottom of the reaction sumptions in both the RD equilibrium and the pervaporation
section (stage 4), while the EtOH etheri(cation is carried models.
 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477 2475

1 0. 5
0. 4 Eqouilibrioum
PV-RD

[-]
0.8 0. 3

Yiel
0. 2 CSTR

d
PFR
0.6
Yield [-]

0. 1 RD
Equilibrium
RD (a) 0
0.4 0. 8
0. 6

-]
Experimental PV-RD data

Yiel [
0.2 Experimental RD data
0. 4
Simulation results

d
Equilibrium
0 0. 2
0 2 4 6 8 10
- 0
Estafe factor, mr /F TAA,0 x10
2 0 5 10
[kg.s/mol] Estafe factor, m
estaf /F x10-2[kg.s/mol]
Fig. 10. TAEE yield as a function of the e factor in RD (b) r TAA,0
−
and PV-RD, RR = 5; Qr = 85 W, FEtOH; 0 = 1:38 × 10 5 mol=s,
Fig. 12. TAEE yield in RD, PFR and CSTR (a) without pervaporation, and
− −
FTAA; 0 = 1:38 × 10 5 mol=s. (b) with pervaporation, PRR=5; Q r =85 W, FEtOH; 0 =1:38×10 5 mol=s,
−
FTAA; 0 = 1:38 × 10 5 mol=s, EtOH feed location: Stage 2, TAA feed
location: stage 3.

1
mixed one obtained at stage 2 in standard conditions. On the
PV-RD other hand, in the absence of pervaporation, the simulated
0.8
yield in RD do not exceed the yield in CSTR and PFR until a
estafe factor higher than 100 and 375 s kg cat=mol, respec-
0.6 tively. Within this range, the reaction rate may be strongly
Yield [-]

retarded by H2Ou and TAEE concentrations in the reaction

section of RD column, than in conventional reactors. In the
0.4
presence of the pervaporation, the required estafe factors to
exceed CSTR increased to 145 s kg cat=mol, while it de-
Experimental PV-RD data
0.2 RD Experimental RD data
creases to 275 s kg cat=mol in PFR. It may be explained by the
ePcient utilization of membrane area against reactant and
Simulation results
product concentrations. The well-mixed condition of re-actants
0 and products in CSTR leads to less reactant diKusion through
0 5 10 15 the membrane than PFR and RD at lower estafe fac-tors.
Reflux cociente [-] Then, the membrane surface area is ePciently utilized to
Fig. 11. Yield prol(lles as a function of re9ux cociente in RD and enhance H2Ou removal and to suppress reactant losses. At
PV-RD,
−5 higher estafe factor values, H2Ou removal is high near the end
mr =FTAA; 0 = 216 kg s=mol, Qr = 85 W, FEtOH; 0 = 0:38 × 10 mol=s,
− of PFR, which can compensate the reactant losses through the
FTAA; 0 = 1:38 × 10 5 mol=s.
membrane at PFR entrance.

8.4. Simulation results on the feed location e:ect 9. Conclusion

and comparison with conventional PFR and CSTR
When the feed components are separated in two
diKerent locations, the lower boiling point reactant (EtOH) is
usu-ally introduced from the lower section of the reaction
sec-tion, and the higher boiling point component (TAA) from
the top. However, this rule cannot be generalized for all
reactive distillation systems. In this case, it is not suitable
due to the fact that TAEE is mainly produced from IA and
EtOH instead of TAA and EtOH. As shown in Fig. 12, a
higher EtOH feed position (stage 2) and a lower TAA po-
sition (stage 3) results a yield, that is 10% higher than the
This work demonstrated the merit of the insertion of
a pervaporation membrane tube into a reactive
distillation col-umn for TAEE etheri(cation:
(1) The pervaporation study has shown the high selectivity
of zeolite membrane NaA for water separation from po-
lareira components, such as alcohols. The separation
was improved at water mole fractions in feed higher
than 10%. The temperature had a positive eKect on the
sep-aration factor.
2476 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477
Xi transformed mole fraction of component i,
(2) The residue curve maps study has shown the dei-
positive eKect of Dá on the dehydration rather mensionless
than the etheri(-cation.
(3) Separate feed component locations with EtOH in
the top of reaction section and TAA in the middle
part increased the contact between EtOH and IA
and favoured the yield of TAEE.
(4) The re9ux cociente eKect was more pronounced
in case of the pervaporation, because H2Ou
inhibition eKect on reaction rates was eliminated.
(5) The reliability of the simulation results was evaluated
by experimental data. Agreements were observed
between the experimentation and the simulation, in
spite of the multiple assumptions made in both of
pervaporation and equilibrium models.

Notation
ai activity of component i, dimensionless
A membrane surface area, m2
Dá Damkohler number, Dá = Qmr k1; ref =Vtot, dei-
mensionless
Fi; 0 feed 9ow rate of component i, mol/s
hi vapor enthalpy of component i in the vapor
phase, J/mol
Ji 9ux of component i in membrane phase,
mol=(s m2)
k reaction rate constant, mol=(s mol H+)
Ki adsorption equilibrium constant of component
i, dimensionless
Keq; j chemical equilibrium constant of reaction j,
dimensionless
Li liquid 9ow rate of component i in the distil-
lation column, mol/s
Llei heat of vaporization, J/mol
mtot total mole number, mol
mr mass of dry ion-exchange resin, kg cat
tot
P total pressure, Pa
sat
Pi saturation pressure of component i, Pa
Peri permeation factor, mol=(s m2)
Q ion-exchange resin capacity, mol H+=kg cat
Qr reboiler heat duty, W
ri intrinsic reaction rate of component i,
mol=(s mol H+)
S membrane surface to vapor 9ow rate in open
distillation, S = A=Vtot, m2 s=mol
T temperature, K
Vi vapor 9ow rate of component i in the distil-
lation column, mol/s
Vtot total vapor 9ow rate, mol/s
xi mole fraction of component i, dimensionless
ei mole fraction of component i in the vapor
phase, dimensionless
ETAEE yield in TAEE, dimensionless

Greek letters

separation factor
%i activity coePcient of component i
dimensionless estafe, d = Vtot dt=mtot
T
i the row vector of the stoichiometric coeP-
cients for component i
T
tot the row vector of the sum of stoichiometric
coePcients

Subscripts

0 feed
p permeate
i chemical species, i
j column stage number, j
sat saturated
tot total

Abbreviations

A15 Amberlyst 15
CSTR continuous stirred tank reactor
ETBE ethyl tert-butyl ether (2-ethoxy-2-methyl
propane)
EtOH ethanol
HETP height equivalent to a theoretical plate
IA isoamylene (2-methyl-2-butene)
MTBE methyl tert-butyl ether (2-methoxy-2-methyl
propane)
NS number of stages
PFR plug 9ow reactor
PV pervaporation
PV-RD pervaporation combined with reactive distil-
lation
PV-CSTR pervaporation combined with continuous
stirred tank reactor
PV-PFR pervaporationcombinedwithplug9owreactor
RD reactive distillation
RR re9ux cociente, dimensionless
TAA tert-amyl alcol (2-methyl-2-butanol)
TAME tert-amyl methyl ether (2-methoxy-2-methyl
butane)
TAEE tert-amyl ethyl ether (2-ethoxy-2-methyl bu-
tane)

Acknowledgements

We are grateful for the supply of zeolite membrane

NaA by Mitsui Engineering & Shipbuilding Co. Ltd.,
Japan. We are also deeply indebted to Mr. H. Itoh for
the technical assistance.
 F. Aiouache, S. Goto / Chemical Engineering Science 58 (2003) 2465 – 2477
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