Fuel Processing Technology 102 (2012) 1–10

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Fuel Processing Technology

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TAEE synthesis from isoamylenes and ethanol by catalytic distillation: Pilot plant
experiments and model validation
C.A. González-Rugerio a,⁎, T. Keller a, J. Pilarczyk b, W. Sałacki b, A. Górak a, c
a
TU Dortmund University, Department of Biochemical and Chemical Engineering, Emil-Figge-Strasse 70, D-44227 Dortmund, Germany
b
Research and Development Centre of Refinery Industry S.A., Chemikow 5, 09–411 Plock, Poland
c
Lodz Technical University, Faculty of Process and Environmental Engineering, Wólczañska 213, 90–924, Lodz, Poland

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

Article history: In this work, the synthesis of tert-amyl ethyl ether (TAEE) from isoamylenes and ethanol by catalytic distil-
Received 27 January 2012 lation (CD) is experimentally and theoretically investigated. As the isoamylenes feedstock for pilot-scale ex-
Received in revised form 13 April 2012 periments, an industrial light gasoline fraction from a fluid catalytic cracking unit was used. Consequently,
Accepted 17 April 2012
the feed stream to the CD column consisted of almost 100 components and approximately 20 chemical reac-
Available online 12 May 2012
tions took place in the column. For modelling purposes, six chemical reactions and 18 components were se-
Keywords:
lected to represent the chemical system. Despite the simplifications carried out in the chemical system, a
gasoline additives good agreement between experimental data and simulation results using a non-equilibrium stage model
octane enhancers was found. The results presented in this paper show the technical feasibility of TAEE production by CD. How-
oxygenate ever, the mole fraction of TAEE in the bottom stream of the column was only 24% due to the presence of heavy
tert-amyl ethyl ether inert components in the column feed. The experimental conditions must be carefully selected, because TAEE
catalytic distillation process modelling decomposition and a high by-products formation occurred if high pressures or D/F ratios were used during
FCC gasoline the column operation.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction of volatile organic compounds are diminished. Furthermore, TAEE

Reactive distillation (RD), in which chemical reaction and distilla-
tion are integrated into one single device, is a well-known alternative
technology to conventional processes with sequential reaction and dis-
tillation steps. The chemical reactions taking place in an RD column can
be either homogeneously or heterogeneously catalysed. In the latter
case, commonly referred as catalytic distillation (CD), the solid catalyst
is immobilised in packing or on trays [1]. CD processes are advanta-
geous when compared to homogeneously catalysed RD ones because
no additional recovering step of the catalyst is necessary [2].
Currently, one of the main applications of CD at the commercial
scale is in the production of gasoline additives such as methyl tert-
butyl ether (MTBE) [3]. This ether is an excellent gasoline-blending
compound due to its high octane number and high oxygen content
[4]. However, groundwater pollution problems associated with the
use of MTBE have been reported [5]; therefore, an increasing interest
exists in the production of other high-octane gasoline compounds to
replace MTBE, such as tert-amyl ethyl ether (TAEE) [6]. TAEE is con-
sidered an attractive oxygenate candidate because it has a low Reid
vapour pressure [7], which is beneficial because gasoline emissions
⁎ Corresponding author. Tel.: + 49 231 755 2682; fax: + 49 231 755 3035.
E-mail addresses: carlos.rugerio@bci.tu-dortmund.de (C.A. González-Rugerio),
tobias.keller@bci.tu-dortmund.de (T. Keller), Janusz.pilarczyk@obr.pl (J. Pilarczyk),
Wieslaw.salacki@obr.pl (W. Sałacki), Andrzej.gorak@bci.tu-dortmund.de (A. Górak).
has lower water solubility than MTBE [8], and therefore, the risk of
groundwater pollution is reduced.
TAEE is formed by the etherification reactions of two isoamylenes
(IA), 2-methyl-1-butene and 2-methyl-2-butene, with ethanol (EtOH)
[9]. The light gasoline fraction from fluid catalytic cracking, referred as
FCC gasoline in this paper, is used as the IA source. IA are highly reactive
in the atmosphere and contribute to photochemical smog formation
[10]. Therefore, it is necessary to remove IA from the FCC gasoline,
which can be achieved through the production of TAEE. Because the
etherification of IA with EtOH is a chemical equilibrium limited reaction,
CD is an attractive technology to overcome the equilibrium conversion.
IA are the most volatile components present in the chemical system (IA,
EtOH and TAEE), and unreacted IA are thus obtained in the distillate
stream while TAEE is the component with the highest boiling point
and it is the bottom product of the CD column.
TAEE synthesis by CD has been experimentally and/or theoretical-
ly investigated by several authors [11-16], but most of these publica-
tions considered a synthetic mixture with only some low boiling
point inert components in the column feed [11-14]. Consequently, it
was possible to obtain TAEE as a pure product in the bottom stream
of the CD column, but for the production of TAEE at commercial
scale, the FCC gasoline is used as a feedstock for IA. FCC gasoline con-
tains almost one hundred components [17], some of which have high
boiling points. Thus, it is not feasible to reach high ether purities in
the CD column. Furthermore, not only IA but also C6 reactive olefins

0378-3820/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2012.04.012
2 C.A. González-Rugerio et al. / Fuel Processing Technology 102 (2012) 1–10

Table 1 The FCC gasoline was mixed with EtOH and fed to a fixed-bed pre-
FCC gasoline composition. reactor. To further increase the IA conversion, the outlet stream of the
Component Mass fraction (wt %) prereactor containing TAEE is subsequently fed to the CD column
(Fig. 1). In this study we focus only on the experimental investigation
IA ≈ 19 – 21
C6 reactive olefins 6 and modelling of the CD column.
C4 inert components 1
C5 inert components (mainly isopentane) 42
C6 inert components 24
2.2. Column setup
C7 and heavier inert components balance

Four experiments were performed in a pilot-plant CD column at

are present in the FCC gasoline [17] and therefore several side reac-
tions occur simultaneously.
In this work, the synthesis of TAEE by CD using industrial FCC gaso-
line is experimentally and theoretically investigated. Due to the high
number of components and chemical reactions that occur during the
etherification reaction, for modelling purposes several simplifications
of the chemical system were carried out. Six chemical reactions and
18 components were considered to represent the FCC gasoline during
simulations performed in this study. Moreover, both equilibrium stage
(EQ) and non-equilibrium stage (NEQ) CD process models are used
and the simulation results are validated with pilot plant experiments.
2. Experimental
2.1. IA source and pre-treatment steps
The feedstock utilised for the experiments was directly obtained
from a refinery. Table 1 shows a typical composition of the FCC gasoline
after a selective hydrogenation was carried out to remove its impurities,
i.e. dienes, which can deactivate the catalyst. Chemical grade EtOH was
used as the reactant.
the Research Centre of Refinery Industry in Poland. The CD column
has an inner diameter of 200 mm and an overall packing height of
4 m (Fig. 1). For the rectifying section, 1 m of the structured packing
Mellapak 750Y® is used. The reactive section contains 1 m of the cat-
alytic packing Katapak SP11® filled with 41 vol % of the catalyst
Amberlyst 47 W. For the stripping section, 2 meters of the packing
Mellapak 750Y® are used. The feed is located just below the reactive
zone to enrich this section with the lowest boiling point components
(IA).
The column is equipped with a total condenser and a vertical
reboiler. Mass flow rates of the feed and bottom streams are mea-
sured using industrial balances via the time derivative of the mass
change, while reflux and distillate flow rates are quantified with a
coriolis-type flowmeter. Process data, such as temperatures, flow
rates, liquid tank levels and pressures are stored and visualised
by a monitoring system based on the microprocessor controller
MSC-68. Steady-state operation of the column is ensured by check-
ing the mass balance in the entire column and temperature at each
measured location. The experimental setup, packing, tanks and
piping are made from stainless steel. To maintain adiabatic condi-
tions, the column is insulated with an 80 mm layer of mineral
wool.

Fig. 1. Experimental setup for TAEE synthesis from EtOH and FCC gasoline. F (flow), P (pressure), T (temperature), L (liquid tank level).
 C.A. González-Rugerio et al. / Fuel Processing Technology 102 (2012) 1–10
Fig. 2. TAEE synthesis reaction network.
2.3. Analytics
Liquid samples were analysed off-line according to ASTM D 5134
[18] and internal OBR/BA/AC-12/96 standards. A gas chromatograph
Hewlett Packard 6890 was used, which is equipped with a capillary
column HP-1 (100 m × 0.25 mm × 0.5 mm) and a flame ionisation
detector. For water detection Karl Fischer titration was applied.
2.4. Experimental conditions
During the experimental investigation different operating param-
eters were varied. In particular, the total feed flow rate was varied be-
tween 380 and 557 mol/h, the molar ratio EtOH/IA in the column feed
between 1.16 and 1.39, the reflux ratio (RR) between 1.49 and 1.84,
the distillate to feed ratio (D/F) between 0.68 and 0.84 mol/mol and
the top column pressure was set to 300 or 400 kPa.
2.5. Data reconciliation
Experimental measurements are always affected by different error
sources (e.g., from sampling and inappropriate calibration); there-
fore, the mass balance in the entire column is not closed. To fulfil
the mass conservation law, data reconciliation was used. In essence,
in the data reconciliation method the experimental concentrations
and molar flow rates are varied within the limits of their experimen-
tal error to satisfy physical constraints such as mass balance and the
mass fraction summation condition. By applying data reconciliation,
the quality of the measurement data is expected to improve. A de-
tailed formulation of the data reconciliation method used in this man-
uscript is given in Appendix A.
3. Chemical system considered for simulations
Industrial FCC gasoline was used as the source for IA and as a con-
sequence, almost one hundred chemical compounds were detected
by gas chromatography during our experiments. Moreover, taking
into account all of these components, at least 20 independent chem-
ical reactions are reported in the literature [10,19,20]. Therefore, for
modelling purposes, some simplifications in the chemical system
Table 2
Chemical equilibrium constants at stoichiometric EtOH/IA and reaction rate constants as a function of temperature [9,21].
Chemical equilibrium constants
T (K) reaction R.1 reaction R.2
323 30.8 2.5
333 21.0 1.9
343 14.5 1.5
353 10.2 1.1
363 7.3 0.9
373 5.2 0.7
3
were performed. Sections 3.1 and 3.2 provide information on the se-
lection of chemical reactions and components for representing the
chemical system during simulations.
3.1. Reaction kinetics
3.1.1. Main reactions: TAEE synthesis
TAEE is produced by the acid-catalysed, exothermic and chemical
equilibrium-limited reactions between the two IA, 2-methyl-1-
butene (2M1B) and 2-methyl-2-butene (2M2B), with EtOH according
to chemical equations R.1 and R.2 (Fig. 2). The isomerisation between
2M1B and 2M2B is an additional chemical equilibrium-limited reac-
tion (equation R.3).
In Table 2, the reaction rate and chemical equilibrium constants
for reactions R.1 – R.3 are given as a function of temperature. From
the information presented in Table 2, it can be observed that the
isomerisation reaction is undesirable in the sense that the fast reaction
R.1 is replaced by the slow reaction R.2 through the isomerisation. Note
that the chemical equilibrium lies strongly on the product side for reac-
tions R.1 and R.3.
The reaction rate equations for the TAEE synthesis with Amberlyst
16 W as the catalyst and based on the Langmuir-Hinshelwood model
were taken from Linnekoski et al. [9].
3.1.2. Side reactions
In addition to the main reactions given above, several side reac-
tions can occur [10,19,20]. Some of these reactions include the dehy-
dration of EtOH to yield diethyl ether and water, the hydration of both
IA to yield tert-amyl alcohol, the dimerisation of the IA and the forma-
tion of tert-hexyl ethyl ethers (THEE) from C6 reactive olefins.
Because neither diethyl ether nor water was found during the exper-
iments, the dehydration of EtOH and all reactions in which water is a
reactant/product were not been considered for modelling purposes.
In contrast, a significant amount of dimers and THEE were detected in
the experiments; therefore, additional reactions to R.1 – R. 3 were in-
cluded in the model to account for the formation of THEE and dimers.
The selected side reactions are discussed in Section 3.1.2.1 and 3.1.2.2.
3.1.2.1. THEE formation. THEE is formed by the exothermic and chemical
equilibrium limited reactions of C6 reactive olefins with EtOH. Zhang
and Datta [19,22] reported seven C6 reactive olefins (Table 3), which
can form three isomers of THEE during etherification with EtOH. In ad-
dition to the etherification reaction, the isomerisation between these
olefins takes place. In our experiments, five of these seven olefins
were detected by gas chromatography and their concentrations in the
prereactor feed stream are shown in Table 3. Note that the total con-
centration of C6 reactive olefins was approximately 6 wt %.
To simplify the reaction scheme for the THEE formation, C6 reac-
tive olefins were lumped and reaction R.4 was selected as representa-
tive of THEE synthesis (Fig. 3). Chemical reaction R.4 was selected
because it is the slowest reaction that produces THEE 1 and the con-
centration of 2-methyl-2-pentene (2M2P) is slightly higher among
the detected C6 reactive olefins. The reaction rate equation for the
THEE synthesis with Amberlyst 15 as the catalyst and based on the
Reaction rate constants (mol∙kg- 1∙s- 1)
reaction R.3 reaction R.1 reaction R.2 reaction R.3
12.1 0.3 0.1 0.1
10.9 0.7 0.2 0.2
9.9 1.6 0.4 0.4
9.0 3.4 1.1 0.8
8.3 6.9 2.7 1.5
7.6 13.7 6.4 2.9
4 C.A. González-Rugerio et al. / Fuel Processing Technology 102 (2012) 1–10
Table 3
Isomers of THEE produced by the etherification of different C6 reactive olefins with
EtOH, (C6 reactive olefin + EtOH ↔ THEE). Adapted from Zhang and Datta [19,22].
C6 reactive olefins Prereactor feed, Ether produced with EtOH
wt %
2-methyl-1-pentene 1.11 2-methyl-2-ethoxy pentane
2-methyl-2-pentene 2.31 (THEE 1)
2,3-dimethyl-1-butene not found 2,3-dimethyl-2-ethoxy butane
2,3-dimethyl-2-butene 1.02 (THEE 2)
Cis-3-methyl-2- 0.89 3-methyl-3-ethoxy pentane
pentene (THEE 3)
Trans-3-methyl-2- 1.34
pentene
2-ethyl-1-butene traces
Langmuir-Hinshelwood-Hugen-Watson model were taken from Zhang
and Datta [19].
3.1.2.2. Dimerisation reactions. Dimers are produced by the exothermic
and irreversible reactions of both IA [10,23]. Several authors have ex-
perimentally found up to eight isomers as the products of the
dimerisation reactions; however, these authors agreed that the iso-
meric mixture of dimers consists mainly of three products, which
are shown in Fig. 4 [10,23]. In particular, in the initial stages of the
dimerisation reaction, dimers selectivity favours the formation of
2,3,4,4-tetramethyl-1-hexene, but as the reaction progresses, it
isomerises to the other two dimers shown in Fig. 4. Low EtOH/IA
molar ratios or high temperatures are favourable conditions for the
formation of dimers [23].
In this study, reactions R.5 and R.6 were included in the model as
representatives of the dimerisation reactions. Because the properties
of dimers were not available in the literature, we used an alkene, 2-
methyl-1-nonene, with the same molecular weight and similar boiling
point to dimers as its equivalent. Reaction rate equations obtained
with Amberlyst 15 as the catalyst were taken from Shah and Sharma
[23]. Kinetic parameters were taken assuming that 2,3,4,4-tetra-
methyl-1-hexene is the main dimerisation product.
2M1B þ 2M1B→Dimers ðC 10 H20 Þ
2M2B þ 2M2B→Dimers
3.1.3. Catalyst
For the pilot-plant experiments, the catalyst Amberlyst 47 W was
immobilised in the reactive section of the CD column. However, the
published reaction rate equations were obtained using either Amberlyst
16 W (TAEE synthesis) or Amberlyst 15 (THEE and dimerisation reac-
tions) as catalysts. Amberlyst 47 W is in essence the same than the com-
monly used Amberlyst 15 W but sieved after the manufacturing process
to guarantee a higher uniformity of the particle size. Because the phys-
ical properties of these catalysts are rather similar (Table 4), the publi-
shed reaction rate equations were assumed to also be valid for the
Amberlyst 47 W used in the present study.
The reaction rate equations for reactions R.1–R.6 that were consid-
ered in the model are given in Table 5. The pre-exponential factors
and activation energy for the Arrhenius equation as well as the chem-
ical equilibrium constants are given in Appendix B.
Fig. 3. Chemical reaction considered during simulations for the synthesis of THEE.
Fig. 4. Main products of the dimerisation reaction [10,23].
3.2. Selection of key inert components
The selection of the key components representing the chemical
system is crucial for the correct analysis of the column performance.
Frequently, in the literature, such a stream is considered using only
some inert components with low boiling points [11-14], although in
industrial streams it has been found that there are several heavier
species present. In our paper, some of these heavy inert components
were considered for modelling purposes.
Inert components were firstly lumped based on the similarity of
their chemical structure (e.g., C4 alkanes were lumped) and each
group was represented by one key chemical compound. The criteria
set for the selection of these key components were based on their
content in the FCC gasoline and on their ability to form azeotropes.
For example, isopentane and 2-methylpentane (2Mthp) were select-
ed as key components because their mass fractions in the prereactor
feed were 22.82 and 11.02%, respectively, and both can form an azeo-
trope with EtOH. Isobutene was not included as a key component be-
cause its mass fraction was only 0.05% and it does not form any
azeotropes with other components. The azeotropes are crucial be-
cause they have a high influence on the column performance [25].
Based on these criteria, 11 inert components were chosen to repre-
sent the chemical system. After this simplification, the key compo-
nents, the groups that they represent and the feed composition to
the CD column are shown in Table 6. This Table also shows the pres-
ence of several inert components with high boiling points that are
obtained in the bottom stream of the CD column.
Fig. 5 summarises the simplifications carried out in the chemical
system for simulations and the criteria set for the selection of compo-
nents. Six parallel and consecutive chemical reactions and 18 compo-
nents (11 are inert species) were considered in the model as
representatives of the chemical system, in which almost one hundred
ðR:5Þ
components are present and more than 20 independent chemical re-
actions take place [10,19,20].
ðR:6Þ
3.3. Thermodynamics
The activity coefficients in the liquid phase were calculated by the
UNIFAC model and the Soave-Redlich-Kwong (SRK) equation of state
was used to estimate the fugacity coefficients. Pure component prop-
erties were taken from the Aspen Properties TM database. Because
THEE was not present in the Aspen databank, the built-in group con-
tribution methods in Aspen properties such as the Joback and Benson
methods [26] were used to estimate the physical properties of THEE.
Despite the simplifications performed in the chemical system, 17
binary and 2 ternary azeotropes, primarily formed with EtOH, are
predicted by the UNIFAC-SRK model at 300 kPa. An overview of
these azeotropes is given in Appendix C.
Table 4
Physical properties of catalysts [24].
Amberlyst Amberlyst Amberlyst
47 W 16 W 15 W
Concentration of active ≥ 1.65 ≥ 1.7 ≥ 1.7
sites (eq/l)
Surface area (m2/g) 50 30 53
Average pore diameter (nm) 24 25 30
Shipping weight (g/l) 770 780 770
Moisture holding capacity (%) 50 – 50 52 -58 52 – 57
 C.A. González-Rugerio et al. / Fuel Processing Technology 102 (2012) 1–10 5

Table 5 Table 6
Reaction rate equations for TAEE synthesis. Composition of the column feed after the components of the FCC gasoline were lumped.

Reaction Reaction rate equation Component name Abbreviation Representing Tb Column feed, xi
(K) (mol/mol)
R.1 r1 ¼ k1 ða2M1B aEtOH aTAEE2=K 1 Þ
ð1þK EtOH aEtOH Þ
Isopentane I-Pent Inert C4 300.9 0.286
R.2 r2 ¼ k2 ða2M2B aEtOH aTAEE2=K 2 Þ components +
ð1þK EtOH aEtOH Þ
isopentane
R.3 r3 ¼ k3 ða1þK
2M1B a2M2B =K 3 Þ
EtOH aEtOH
N-pentane N-Pent Inert C5 309.1 0.041
R.4 r4 ¼ k4 ða2M2P a′EtOH aTHEE2=K 4 Þ components
ð1þK EtOH aEtOH Þ 2-methyl-2- 2M2P C6 reactive olefins 340.1 0.028
R.5 r5 = k5C2M1B pentene
R.6 r6 = k6C2M2B Trans-2-hexene Trans2h Inert C6 341.1 0.028
components
Methylcyclopentane Mthcycp Inert C7 344.9 0.036
components
3.4. CD process model
2-methyl-2-ethoxy THEE Three isomers of 417.1 0.010
pentane THEE
A reliable CD process model is necessary to analyse the CD column 2-methyl-1-nonene Dimers Dimers 441.4 0.005
performance, to design the column or to optimise the CD process ef- 8-methyl-1-nonene C10 C8 and higher inert 443.6 0.001
ficiency. In the literature, several mathematical models to represent components
2-methyl-1-butene 2M1B - 304.2 0.012
the phenomena occurring in a CD process have been presented [27- Trans-2-pentene Trans2p - 309.4 0.084
29]. These models can be primarily classified as either equilibrium Cis-2-pentene Cis2p - 310 0.035
stage (EQ) or non-equilibrium stage (NEQ) models. However, the 2-methyl-2-butene 2M2B - 311.6 0.091
choice of the appropriate model is not trivial and has to be checked Cyclopentane Cycp - 317.3 0.036
2-methylpentane 2Mthp - 333.3 0.073
for each separation task using experimental data. Within the scope
3-methylpentane 3Mthp - 336.3 0.038
of this work, both an EQ model taking into account the reaction kinet- N-hexane N-Hexan - 342.1 0.010
ics and an NEQ model using the Stefan-Maxwell approach are applied. Ethanol EtOH - 351.3 0.132
Tert-amyl-ethyl ether TAEE - 374 0.054
3.4.1. EQ model
In the EQ model, it is assumed that the vapour and liquid streams The heterogeneously catalysed reaction was described by a
leaving each ideal tray are at thermodynamic equilibrium with each pseudo-homogeneous approach in which the mass transfer resistance
other. The departure from equilibrium is taken into account by the between the liquid phase and the solid catalyst is neglected. This as-
tray efficiency or by the height equivalent to a theoretical plate for sumption has been verified for the synthesis of tert-amyl methyl
packed columns [30]. The EQ model is widely used due to its simplic- ether (TAME) by Sundmacher et al. [36]. Because the reaction rates
ity when compared to the NEQ model, which is advantageous in cases for TAEE are slower than for TAME, the pseudo-homogeneous ap-
where the computing time could be extensive. proach can also be applied for the TAEE synthesis.
Information about the separation efficiency of Mellapak 750Y® and More details about the applied models, which were implemented
Katapak SP11® is already available in the literature [31,32]. The number into the Aspen Custom Modeler TM simulation environment, can be
of theoretical stages per meter for the noncatalytic packing of Mellapak found in the work of Klöker et al. [29].
750Y® is 5 m - 1 while for the catalytic one it is 2 m - 1. The CD column Note that in both the EQ and NEQ models, all model parameters
was simulated using 17 equilibrium stages (5 for the rectifying section, such as VLE data, reaction kinetics, correlations to estimate mass
2 for the catalytic zone and 10 for the stripping section), a total con- transfer coefficients in the case of the NEQ model, etc. are taken
denser and a partial reboiler giving a total of 19 equilibrium stages. from the literature; therefore the, models are fully predictive and do
not need subsequent adjustment of model parameters.
3.4.2. NEQ model
In contrast to the EQ model, in the NEQ model it is assumed that
thermodynamic equilibrium occurs only at the vapour-liquid inter- 4. Results and discussion
face. The actual multicomponent mass and heat transfer rates are
considered. Correlations from Rocha et al. [33,34] were used to esti- 4.1. Experimental results
mate the mass transfer coefficients in the vapour and liquid phases,
the effective interfacial area, the liquid hold-up and the pressure Table 7 shows the reactant conversions, product yields and ether
drop in the non-catalytic packing Mellapak 750Y®. For the catalytic mole fractions in the bottom stream of the CD column that were
packing Katapak SP11®, correlations from Brunazzi and Viva [35] obtained experimentally. In Fig. 6, the experimental compositions
were used. The CD column was discretised in the axial direction and along the column height are shown for Exp 1, while in Fig. 8, the exper-
simulated using 54 discretes (16 for the rectifying section, 7 for the imental temperatures for all experiments are given. In both Figures, ex-
catalytic zone and 31 for the stripping section). The reboiler and perimental data are represented by symbols. Similar profiles were
total condenser were assumed to be ideal stages. obtained for the remaining experiments. The complete reconciled

Fig. 5. Characteristics of the chemical system in the experiments and in the simulations.
6 C.A. González-Rugerio et al. / Fuel Processing Technology 102 (2012) 1–10

Table 7 high concentration of heavy inert components present in the chemical

Experimental conditions and results. system. These inert species also leave the column in the bottom stream
Exp 1 Exp 2 Exp 3 Exp 4 and thus reduce the TAEE purity. In contrast to the low TAEE purity
found in this work, Everson et al. [11] and Ciornei et al. [12] reported
Experimental conditions
Feed flow rate (mol/h) 380.10 364.44 399.29 557.28 TAEE purities of 80 and 95 mol %, respectively in their studies. However,
D/F (mol ⋅ h− 1/mol ⋅ h− 1) 0.79 0.74 0.68 0.84 these authors considered only inert components with low boiling
RR 1.71 1.49 1.84 1.71 points, which does not provide a proper representation of the FCC gas-
Molar ratio EtOH/IA in the column feed, (mol/mol) 1.31 1.26 1.16 1.39
oline as shown in the present contribution.
Operating pressure (kPa) 400 300 300 400
TAEE decomposition was detected in Exp 1 and 4 as a consequence
Experimental results of increasing the temperature in the catalytic zone. At high tempera-
IA conversion (%) 7.76 11.48 32.08 - 1.00 tures the forward reaction for the TAEE synthesis becomes slower
2M2P conversion (%) 4.85 5.15 8.80 32.98 than the backward reaction because it is exothermic [9]. The incre-
EtOH conversion (%) − 4.46 7.64 20.22 0.07
ment in temperature in Exp 1 and 4 occurred as a result of operating
xTAEE in bottom stream 0.224 0.240 0.248 0.259
xTHEE in bottom stream 0.039 0.044 0.041 0.127 the column at high pressures or D/F ratios. Table 7 indicates that pres-
xDimers in bottom stream 0.046 0.022 0.040 0.054 sures of 400 kPa are adverse to the TAEE production because the
TAEE production (mol/h) − 2.53 2.95 8.32 − 5.24 chemical equilibrium is shifted towards the reactant side. High D/F
THEE production (mol/h) − 0.21 0.53 1.13 4.81
ratios decrease the IA and EtOH loss in the bottom stream of the col-
Dimers production (mol/h) 2.12 0.57 2.58 1.99
Average temperature in the reactive zone (K) 364.2 351.8 349 368.2 umn, while increasing the formation of by-products, increasing TAEE
loss in the distillate stream and resulting TAEE decomposition.
In all experiments a molar ratio of EtOH/IA that was greater than one
experimental data are available online as supplementary material to the in the column feed was used. Under this condition, the etherification of
electronic version of this article, i.e., compositions in the outlet streams IA is favoured in comparison to their dimerisation [23]. It is interesting to
and temperatures along the column height. note that in Exp 4 the molar ratio of EtOH/IA was the highest of all exper-
In all experiments the concentration of IA in the bottom of the CD iments and that even in this case, the dimerisation reaction was higher
column have values below 0.02 mol % and are thus negligible. than the etherification. Operating conditions must be selected in such
Unreacted EtOH is recovered in the distillate stream due to the minimal a way that a high molar ratio of EtOH/IA in the catalytic zone is ensured.
boiling point azeotrope formed between EtOH and the inert compo- The highest IA conversion occurred when the CD column was op-
nents. A short rectifying section is enough to prevent TAEE loss in the erated at low D/F ratio and pressure but at high RR (Exp 3). However,
distillate stream. The concentration of TAEE in the bottom product of the IA conversion achieved was only 32%, which is a consequence of
the column is relatively low, with an average value of 24 mol %. Reasons the slow reaction rate for TAEE. Therefore, a large amount of catalyst
for the low TAEE purity are the low IA conversion (see Table 7) and the would be necessary to reach higher conversions.

Fig. 6. Comparison of experimental (dots) and simulated (lines) composition profiles in the liquid-phase for Exp 1. Simulated data were obtained using the NEQ model.
 C.A. González-Rugerio et al. / Fuel Processing Technology 102 (2012) 1–10
Fig. 7. Parity plot of the experimental and simulated molar fractions obtained with the
NEQ model of all experiments.
The results shown in Table 7 demonstrate the technical feasibility
of the production of TAEE by CD. However, they also indicate that the
operating conditions must be carefully selected because high pres-
sures or D/F ratios will result in TAEE decomposition.
4.2. Model validation
In Fig. 6, the composition profiles obtained with the NEQ model are
compared with the corresponding experimental data of Exp 1. In gener-
al, the model predicts the actual process behaviour with excellent
agreement for the main components (IA, EtOH and TAEE). More signif-
icant deviations appeared in the composition profiles of the inert hydro-
carbons, which can be explained by the fact that the selected
components represented a variety of different species in the industrial
mixture during simulations. Slight deviations for the composition of
THEE and dimers were found at the bottom of the column. These devi-
ations are a consequence of the number of side reactions considered
in the model, i.e., we considered only three side reactions during simu-
lations but at least 20 reactions can take place. However, the significance
of these deviations was rather limited for the description of the process.
The validation based on the remaining pilot plant experiments gave
Fig. 8. Comparison between experimental temperature profiles (dots) with simulation
results (lines) calculated with the NEQ model of all experiments.
7
Fig. 9. Experimental temperature profile (dots) for Exp 4 is compared with NEQ model
results considering side reactions (continuous lines) and without considering the side
reactions (dashed lines).
similar results and confirmed the reliability of the model. The agree-
ment between experimental compositions and the NEQ model results
for all experiments can be observed in the parity plot (Fig. 7). In general,
the model predicts the experimental compositions with a maximum ab-
solute deviation of ± 15%, which is an acceptable value considering the
high complexity of the chemical system and that no parameters in the
model were fitted from experimental data. In Fig. 8, the temperature
profiles obtained with the NEQ model are compared with the experi-
mental values considering all experiments. The model predicts experi-
mental temperatures with an average relative deviation of 1%. The
comparison between the NEQ model results and the experimental
data for all experiments is available online as supplementary material.
4.3. Effect of the side reactions in the model results
To investigate whether the side reactions can be neglected during
the modelling, simulations of the four experiments were performed
without the side reactions, i.e., formation of THEE and dimers were not
considered. A comparison between the experimental temperatures
and the temperatures predicted with the NEQ model for Exp 4 is
Fig. 10. Comparison of liquid phase molar fractions between EQ (dashed lines) and
NEQ (continuous lines) models with experimental data (dots) for Exp 1.
8 C.A. González-Rugerio et al. / Fuel Processing Technology 102 (2012) 1–10

shown in Fig. 9. In this Figure, the symbols represent experimental data, stream of the CD column can be directly used for gasoline blending pur-
the continuous lines represent model results including the side reactions poses as long as environmental requirements are met.
and the discontinuous lines represent the model results without the side Due to the high number of components and chemical reactions
reactions. As expected, a significant difference of up to 10 K between the that can occur during the etherification reaction of IA with EtOH, sev-
experimental temperature and simulated data occurred in the reboiler eral simplifications of the chemical system were carried out for
when the side reactions were not considered. Similarly, Sundmacher modelling purposes. Six chemical reactions and 18 components
et al. [36] and Kolodziej et al. [37] found considerable deviations be- were considered to represent the chemical system during the simula-
tween experimental data and model results for the bottom temperature tions performed. The criteria set for the selection of components were
in some of their experiments. These authors detected the formation of their a) reactivity, b) chemical structure, c) mole fraction in the col-
dimers in some experimental conditions but did not perform simula- umn feed and d) formation of azeotropes. For the CD process simula-
tions including the side reactions. In general, the model will provide tion, two models of different complexity were tested, namely the EQ
poor results, particularly in cases such as those shown in Exp 4, in and the NEQ. The comparison between experimental data and
which the formation of THEE and dimers is significant (Table 7). In model results showed that the NEQ model predicts the experimental
Exp 3 the formation of TAEE is much higher than the production of composition profiles with a higher accuracy than the EQ model. The
THEE and dimers, and therefore the deviations between experimental latter model should be used only in the first steps of the design task.
data and model results becomes smaller. The IA conversion predicted Simulation results without the consideration of the side reaction
by the model without the side reactions is up to 10% lower than the presented important differences when compared to experimental
one obtained when the side reactions were considered. The cause of data. Therefore, the side reactions cannot be neglected during simula-
the lower IA conversion is the dimerisation reaction, as this reaction tions. For optimisation or design purposes, it is necessary to use a val-
is not reversible, i.e. dimers are always produced, the calculated IA idated model that considers the actual industrial conditions, i.e., a
conversion is higher when the side reactions are considered. The re- model that accounts for the side reactions and feed impurities. Such
sults presented in this section show the importance of considering a model was presented in this paper.
the side reactions during simulations. Considerable differences be-
tween experimental and simulated data were found when side reac- Abbreviations
tions were neglected and the formation of THEE and dimers in the
column was significant. 2M1B 2-methyl-1-butene
2M2B 2-methyl-2-butene
4.4. Influence of the modelling depth 2M2P 2-methyl-2-pentene
CD catalytic distillation
In the preceding sections, all model results presented were obtained D/F distillate to feed ratio
using a rigorous NEQ model. In this chapter, a simplified modelling EQ equilibrium stage
depth, namely the EQ model, is applied and compared with the NEQ EtOH ethanol
model and experimental data. Fig. 10 shows the composition profiles Exp experiment
predicted with these two models as well as the experimental composi- FCC fluid catalytic cracking
tions for some selected components using the experimental conditions IA isoamylenes
of Exp 1. The EQ model showed larger deviations than the NEQ for the MTBE methyl tert-butyl ether
compositions above and below the catalytic zone when compared to NEQ non-equilibrium stage
experimental data. The differences in the simulated concentrations RD reactive distillation
using both models were particularly large for the components with a RR reflux ratio
high concentration along the column height, e.g., 2Mthp. A comparison TAEE tert-amyl ethyl ether
in temperatures showed that those predicted for the EQ model were TAME tert-amyl methyl ether
lower than the temperatures predicted for the NEQ model. The differ- THEE tert-hexyl ethyl ether
ence between the EQ and NEQ model results is an indication of mass UNIFAC UNIversal Functional Activity Coefficient
transfer resistances at the vapour-liquid interface, which are not consid- VLE vapour-liquid equilibrium
ered by the EQ model. However, both models were able to predict ex-
perimental compositions in the outlet streams with similar accuracy Notation
and therefore similar reactant conversion levels were obtained. As
pointed out by Taylor and Krishna [27], the final decision on whether Latin letters
the application of a rigorous NEQ model is necessary for a particular ai activity of species i (mol ⋅ mol - 1)
chemical system should be supported by a comparison of model results Ci molar concentration of component i (kmol ⋅ m − 3)
with experimental data measured over the column height. Ei energy activation for reaction i(kJ ⋅ mol - 1)
In the case of TAEE synthesis, our results suggest the importance of KEtOH adsorption equilibrium constant for TAEE synthesis (−)
the application of an NEQ model and the consideration of side reactions K′EtOH adsorption equilibrium constant for THEE synthesis (−)
and impurities in the column feed stream for optimisation and design k0i pre-exponencial factor for the Arrhenius equation for reac-
purposes. The EQ model should only be used in the first steps of the de- tion i (mol ⋅ kg - 1 ⋅ s - 1)
sign task. ki reaction rate constant for reaction i (mol ⋅ kg - 1 ⋅ s - 1)
Ki chemical equilibrium constant for reaction i (−)
5. Conclusions nc number of components (−)
n_ i;bottom molar flow rate of component i in the bottom (mol ⋅ h - 1)
In this work, pilot-scale experiments for TAEE synthesis by CD were n_ i;distillate molar flow rate of component i in the distillate (mol ⋅ h - 1)
performed using industrial FCC gasoline as the feedstock. Experimental n_ i;f eed molar flow rate of component i in the feed (mol ⋅ h - 1)
results demonstrated the technical feasibility of the production of TAEE nm number of measured values (−)
by CD. However, the results also showed that the experimental condi- nreaction number of reactions (−)
tions must be carefully selected because TAEE decomposition occurred n_ total total molar flow rate (mol ⋅ h - 1)
under conditions of high pressures or D/F ratios used during the opera- ri reaction rate (mol ⋅ kg - 1 ⋅ s - 1)
tion of the column. Although pure TAEE is not obtained, the bottom T temperature (K)
 C.A. González-Rugerio et al. / Fuel Processing Technology 102 (2012) 1–10 9

Tb boiling temperature (K) A.2. Application

xi molar fraction of component i in the liquid phase (mol ⋅ mol- 1)
zi, exp experimentally measured value (−) To apply data reconciliation, the 18 selected components were
zi, reconciled reconciled measurement value (−) used. Because reactions R.1-R.6 are not linearly independent, only
five reactions were used, i.e., reaction R.3 was not considered.
The raw data presented an average absolute deviation in the mass
Greek letters conservation law for the inert components of 5%, i.e., inert molar flow
ϕ objective function of the data reconciliation problem (−) rates in the inlet ≠ inert molar flow rates in the outlet by approximately
σi standard deviation of measurement value i (−) 5%. These deviations were corrected by the application of data reconcil-
νi, j stoichiometric coefficient of component i in reaction j (−) iation. Note that the application of this method does not only change
the measurement values in the outlet streams but also in the feed
stream. Thus, the simulations were performed using these reconciled
Acknowledgements feed streams. After data reconciliation was applied, the average relative
deviation between the measured and the reconciled total molar flows
C.A. González-Rugerio is thankful to CONACyT-DAAD for financial and mole fractions were 4% and 9%, respectively.
assistance during the course of this work.

Appendix A. Data reconciliation Appendix B. Kinetic parameters

A.1. Mathematical formulation The adsorption equilibrium constants are given by KEtOH = 3.75E -
3exp(- 2369.5/T) for TAEE synthesis and K′EtOH =2.75 for THEE synthesis.
Assuming that the experimental errors show a distribution with
zero mean and known variance, data reconciliation can be formulated Table B.1
as a constrained weighted least squares optimisation problem [38]. Pre-exponential factors and energy activations for the Arrhenius equation; *units in s− 1.
The objective function, ϕ, defines the weighted sum of squares of the Reaction k0i(mol ⋅ kg- 1 ⋅ s- 1) Ei(kJ/mol)
adjustments to all nm measurements and is given in Eq. (A.1), where
R.1 7.82 E11 76.8
zi, exp is the experimental value, zi, reconciled is the reconciled value and
R.2 1.72 E14 95.9
σi is the experimental standard deviation for each measurement: R.3 4.66 E10 72.9
R.4 1.42 E15 108.7
 2 R.5* 3.03 E3 50.6
X
nm zi;exp  zi;reconciled R.6* 3.03 E3 50.6
ϕ ¼ min ; i ¼ nm ðA:1Þ
i¼1
σ 2i
Table B.2
Coefficients for the calculation of chemical equilibrium constants; lnK i ¼ Ai þ BTi þ
Subject to: C i lnT þ Di T þ Ei T 2 þ F i T 3 ; K 3 ¼ KK 12 :.

Reaction Ai Bi Ci Di Ei Fi
X
nreaction
n_ i;f eed  n_ i;distillate  n_ i;bottom þ νi;j r i;j ¼ 0 i ¼ 1; …nc ; j ¼ 1; …nreaction R.1 22.809 3136.3 − 5.8227 0.0179 −6.395 E-6 − 1.672 E-8
j¼1
R.2 26.779 2078.6 − 6.5925 0.0231 −1.126 E-5 − 1.414 E-8
R.4 − 84.4308 6870.67 13.0318 − 0.03783 3.3181 E-5 −3.2602 E-8
ðA:2Þ

Appendix C. Azeotropes
X
nc
xi ¼ 1 f or each stream ðA:3Þ
i¼1 Associated content

The standard deviation corresponds to the uncertainty in the mea- Supporting Information available:
sured variable and must be experimentally determined or specified to Table C.1
a reasonable value. In the case of the experimental determination of Azeotropes present in the chemical system (predicted by the UNIFAC model at 300 kPa).
mass fractions, we considered two different measurement errors: an Component 1 Component 2 Component 3 x1 x2 Tb (K)
absolute error of± 0.015 g ⋅ g − 1 was assumed if the experimental (mol/mol) (mol/mol)
mass fraction is larger than ± 0.1 g ⋅ g − 1. Otherwise, an absolute error EtOH I-Pent - 0.112 0.888 334.1
of ± 0.01 g ⋅ g− 1 was considered. EtOH 2M1B - 0.106 0.895 338.0
During data reconciliation, the measured variables are varied EtOH N-Pent - 0.157 0.843 341.1
within the limits of the experimental error (Eq. (A.4)) such that phys- EtOH Trans2p - 0.149 0.852 342.4
EtOH Cis2p - 0.154 0.846 343.1
ical constraints are fulfilled. If these limits are exceeded, other more
EtOH 2M2B - 0.162 0.838 344.3
robust optimisation methods should be used. For the CD process, N-Pent Trans2p - 0.485 0.515 344.8
the control volume for data reconciliation is the entire column. N-Pent Cis2p - 0.762 0.238 345.1
EtOH Cycp - 0.240 0.760 351.3
 2 EtOH 2Mthp - 0.346 0.654 358.4
2
zi;exp  zi;reconciled ≤σ i i ¼ nm ðA:4Þ EtOH 3Mthp - 0.371 0.629 360.3
EtOH N-Hexan - 0.416 0.584 363.4
EtOH 2M2P - 0.416 0.584 363.7
EtOH Mthcycp 2M2P 0.415 0.074 363.7
Eqs. (A.2) and (A.3) define the set of model constraints to be sat- EtOH Mthcycp Trans2h 0.427 0.015 363.9
isfied by the reconciled values. If the CD column is at steady state, EtOH Trans2h - 0.427 0.573 363.9
the component molar balance must be satisfied for both inert and re- EtOH Mthcycp - 0.434 0.566 364.6
active species (Eq. (A.2)). Additionally, the summation condition of N-Hexan Trans2h - 0.013 0.987 380.1
EtOH TAEE - 0.813 0.187 380.1
the mole fractions must be fulfilled for all streams (Eq. (A.3)).
10 C.A. González-Rugerio et al. / Fuel Processing Technology 102 (2012) 1–10
- Experimental compositions in the outlet streams and NEQ model
results
- Experimental temperatures and simulation results obtained with
the NEQ model
Appendix D. Supplementary data
Supplementary data to this article can be found online at http://
dx.doi.org/10.1016/j.fuproc.2012.04.012.
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