Catalytic Distillation Process Modelling and Simulation for the TAEE

Synthesis on Amberlyst35

Ciornei Cristian1, Bumbac Gheorghe1, Plesu Alexandra1, Motelica Anatolie1, Ivanescu

Ion2, Toma Aurelian3
1
University Politehnica of Bucharest, Centre for Technology Transfer in the Process Industries,
1, Polizu Street, Building A, Room A056, Sector 1, RO-011061, Bucharest, Romania,
Phone: +40-21-4023916, Fax: +40-21-3185900, email: [email protected]
2
S.C. PETROM S.A., Calea Dorobanti No. 239, Bucuresti, ROMANIA, Phone:+40-21-4060319,
E-mail: [email protected]
3
S.C. PETROM S.A, INCERP Ploiesti Subsidiary, 291A, Republicii Blvd., RO-100072 Ploiesti,
Romania, Phone: +40-244-598738, Fax: +40-244-598732, email: [email protected]

Abstract
Catalytic distillation (CD), a more integrated reaction and separation process, is possible and
beneficial when both volatility of reactants is close each other, but quite different from the
volatility of products and reaction inert compounds, and the chemical reaction conversion is
limited by chemical equilibrium. Synthesis of tertiary ethers such as tert-amyl-methyl-ether
(TAME) and tert-amyl-ethyl-ether (TAEE), from C5 reactive alkenes which are available in FCC
light gasoline, with methanol or ethanol respectively, are a very important processes for ecologic
gasoline blending. The production of tertiary ethers is one of most interesting fields of
application of catalytic distillation (CD) processes. In the synthesis of these tertiary ethers, either
methanol or ethanol reacts with iso-alkenes in the presence of acidic catalysts, such as Amberlyst
class ion exchange resins. For conceptual design of the industrial process, or for a safe operation
of such a complex multifunctional apparatus as a catalytic distillation column, it is necessary to
analyse the process behaviour based on a reliable mathematical model. In this contribution a
model including kinetic effects of chemical reaction is built. Simulation work is performed for
specific operating conditions using HYSYS simulation environment. In order to simulate the
CD column this was represented as an ensemble of three components corresponding to the
software chemical operation unit modules available in HYSYS (Bozga et al., 1999).

Keywords: catalytic distillation, TAEE synthesis, process modelling, process simulation,

reaction kinetics

Introduction
Oxygenated hydrocarbon compounds as tertiary ethers and alcohols play an important role in
ecological gasoline blending. Tertiary ethers were obtained treating with aliphatic alcohols the
olefins contained in FCC gasoline. First industrial scale application of this type of process was
synthesis of MTBE (methyl tertiary-butyl ether). Then other tertiary ethers were considered e.g.:
ETBE (ethyl-tertiary butyl ether), TAME (tert-amyl methyl ether) and TAEE (tert-amyl ethyl
ether). This procedure reduces substantially the olefin content of gasoline. TAEE can be obtained
industrially in two steps: reaction mixture passes firstly through a fixed bed pre-reactor when
conversion nearly those of equilibrium are obtained. Then, the reaction is completed in the CD
column.
Catalytic distillation, involving reaction and separation to take place in the same unit, is possible
and beneficial when volatility of reactants is close and quite different from the volatility of
products and when the conversion is limited by chemical equilibrium (Doherty et al., 2001).
Synthesis of TAEE from ethanol and iso-amylenes fits to this conditions. In the case of TAEE
synthesis, the reaction is taking place on the surface and/or in the pores of the catalyst grains
(cationic exchange resin Amberlyst). Since TAEE is an important additive for ecological
gasoline, modelling and simulation of kinetics and operation of TAEE synthesis is an important
practical problem. Commercial process simulators have scarce means for the simulation of
catalytic distillation columns. We propose a solution to adapt the resources of HYSYS 3.0.1
simulation environment to solve this kind of process unit. A conceptual model was generated in
HYSYSTM, for a catalytic distillation column with Sulzer KATAPAK structured packing,
containing Amberlyst 35 ion exchange resin. In the catalytic distillation column model, three
zones were considered: the stripping zone (simulated as the reboiled absorber standard
HYSYS operation), the reaction-separation zone and the rectifying zone (simulated as refluxed
absorber standard HYSYS operation). The reaction separation zone is modelled considering
the back-flow cell model (BCM) with forward flow of the liquid and backward flow of the
vapour. The BCM consist of series of five continuous stirred tank reactor units (CSTR) with the
same geometry and size (Bozga et al., 2003). In each cell of the series is assumed to reach the
vapour-liquid equilibrium, the increase of conversion being calculated as in a CSTR reactor.
Both stripping and the rectifying zones are represented as non-catalytic packed columns. The
simulation is performed using UNIQUAC-UNIFAC model property package to calculate the
activity coefficients in the liquid phase. The model simulation results are compared with pilot
plant experimental data on TAEE synthesis by catalytic distillation.
In this paper, we focused on the relevance of the commercial software HYSYS for the
simulation of catalytic distillation columns. As in the current version of HYSYS the built-in
CD module is not directly suitable for the simulation of the heterogeneous catalytic distillation
process, this study is concentrated to develop a model for CD and to implement it in the
HYSYS simulation environment. The objectives of this work are to develop a suitable
simulation module for heterogeneous reactive distillation compatible with HYSYS and to
apply results to design scale pilot plant unit.
The simulated process scheme includes a pre-reactor (adiabatic tubular fixed bed
reactor) and the reactive distillation column. The advantage of using a pre-reactor for TAEE
synthesis is to insure a partial transformation of reactants before CD column, thus increasing the
throughput of reaction system.

Reaction kinetics and thermodynamics

Main reactions for TAEE synthesis are presented below.

EtOH (liq )  2M1B(liq )  TAEE (liq )

ethanol 2  methyl butene 1 tert  amyl ethyl ether
(I)

EtOH (liq )  2M 2B(liq )  TAEE (liq )

ethanol 2  methyl butene  2 tert  amyl ethyl ether
(II)

2M1B (liq )  2M 2B (liq )

2 methyl butene 1 2 methyl butene  2
(III)

Both etherification reactions are exothermic, i.e. the equilibrium isoamylenes conversion to
TAEE decreases with temperature. The isomerisation reaction at operation temperature (between
60°C and 90°C – the upper limit of temperature to preserve catalyst activity) favours the 2M2B
formation and this component will have the greatest concentration in the reaction mixture. From
kinetic point of view this situation is not advantageous because a higher reactivity amylene
(2M1B) is replaced by a lower reactivity one (2M2B). The two olefins (2M1B and 2M2B) used
in the synthesis are fed as a hydrocarbon mixture resulted as the C5 fraction from Fluid Catalytic
Cracking (FCC) unit. In Table 1 the composition of the feeding mixture used in the simulated
process scheme is presented. Since ethanol associates almost all hydrocarbon components into
simple and complex azeotropic pairs, the system shows strong non-ideal properties. The property
package used to calculate the liquid activities of the considered components is based on
UNIQUAC-UNIFAC model.
Keeping, for the reaction zone certain operating conditions, secondary reactions can be avoided
(e.g. intermolecular dehydration of ethanol, isoamylenes hydrolysis). In this study we used the
following reaction rate expressions published by Bumbac et al.(2006), valid for Amberlyst35
cationit as a catalyst. Kinetic model include the chemical transformation and also the mass
transfer (reaction components diffusion). Thermodynamic model is mentioned in the same
source.

Process flowsheet
In figure 1 TAEE synthesis process flowsheet using catalytic distillation is presented.
The C5 fraction is mixed with ethanol and the resulting stream is fed to the pre-reactor (IV).
Task of prereactor is to reach chemical reaction equilibrium at its outlet. Then the resulting
mixture is fed to a CD column, below the reaction zone.

Figure 1. Simplified flowsheet for CD column.

The three zones of the CD column are represented in the flowsheet as three different
units. The stripping zone of the column is simulated as reboiled absorber, a standard operation in
HYSYS.
The flow and mixing in the reaction zone is approximated by a backflow cell model
(BCM) with forward flow of the liquid and a back flow of vapour in the reactive part of RD zone
(Roemer and Durbin, 1967). The BCM consists in a perfectly mixed cells series (a series with 5
CSTRs). In the cell the conversion increase was calculated considering uniform distribution of
the catalyst in the liquid phase of the cell series and vapour-liquid equilibrium. The adapted
kinetics for the HYSYSTM simulator was checked through simulation of experimental plug-flow
reactor. The computed conversion was found to be in good agreement with experimental
conversion.
The third part is another pure mass transfer unit, representing the rectifying zone of the
reactive distillation. This zone is simulated as refluxed absorber a HYSYS standard operation.

Figure 2 Simulated conversions compared with experimental conversions

Simulated pilot plant characteristics

The main characteristics of the simulated pilot plant are the following: volume of catalyst in the
pre-reactor 200 ml; volume of catalyst in the column 225 ml; diameter of the catalyst pellets
considered as spheres 1mm; column diameter 0.15 m; column rectifying zone packing height
0.64 m (HETP: 0.1 m); column stripping zone packing height 0.48 m (HETP: 0.1 m); the height
of the reactive zone of column 0.9 m (HETP: 0.4 m).

Results and discussion

The feed stream composition used in simulation is presented in Table 1. It consists in 21 C4-C6
hydrocarbons. The mass flowrate of the feed stream is 55.56 kg/h. The operating pressure of
prereactor and CD column is of 3.5 barg.
Figure 3 represents temperature profile in the column. Composition profiles of reactive species
are presented in figure 4 for the liquid phase. The distillate flowrate is 44.72 kg/h and the product
flowrate is 10.94 kg/h.
 Table 1 Composition of the feeding mixture
Component % weight
Butane 1.46
3 methyl butene-1 1.49
Isopentane 44.52
Pentene-1 3.56
2 methyl butene-1 7.19
n-pentane 4.58
Isoprene 0.31
Trans pentene-2 6.94
Cis pentene-2 3.73
2 methyl butene-2 9.32
2,2diMe-butane 0.26
Cyclopentene 1.06
( 4 methyl + 3 methyl ) pentene-1 0.31
Cyclopentane 0.40
2,3 dimethyl butane 0.81
2 methyl pentane 1.63
3 methyl pentane 0.16
2 methyl pentene-1 0.10
n-hexane 0.01
3 methyl cis pentene-2 0.01
Cyclohexene 0.15
Ethanol 12.00

Table 2 Distillate and product composition

Distillate Product
Component composition, composition,
weight fractions weight fractions
Isopentane 0.592225 0.011064
2 methyl butene-1 0.010205 0.000423
2 methyl butene-2 0.046755 0.012678
Ethanol 0.052314 0.017540
TAEE 0.000000 0.919994

Temperature profile is quite smooth in the rectifying and reaction zones. Maximum temperature
for protecting catalyst life is observed. In stripping zone the temperature profile is very steep,
corresponding to separation of very different boiling point compounds (amylenes, hydrocarbons,
TAEE). The composition profile for amylenes presents constant values in the rectifying and
reaction zones corresponding to the necessities of the chemical reaction. Ethanol has a strong
variation, exhibiting a maximum to the middle of the stripping zone as a source for the reactive
zone. TAEE is progressively accumulating in the CD column bottoms due to low volatility.
 Figure 3 CD column temperature profile

Figure 4. CD-Column liquid phase composition profiles

Several simulated values of flow rates, temperatures and concentrations are presented in Table 2
for a set of representative operating conditions. The simulation results with HYSYS for the
TAEE synthesis reactive distillation module set-up, presented in this work, allows to draw the
following conclusions:
- From the chemical transformation point of view it is profitable to place the reaction zone
as close as possible to the top of the column. However, above the reaction zone a
minimal separation zone is needed to separate TAEE from the distillate.
- It is recommended to place the column feed bellow the reaction zone in order to ensure
high reactants concentrations in this zone (as they are more volatile comparing with the
reaction product).

Conclusions
This paper presents a theoretical study for the modelling of reactive distillation column operation
in TAEE synthesis. The quality of the results obtained in this paper is limited by the uncertainty
introduced by the phase hydrodynamics in the reaction zone and the phase equilibrium
hypothesis. The authors foreseen additional studies in order to better describe phase
hydrodynamics, mass transfer outside and inside the catalyst pellets and their influence on
process performances.

References
Bozga, G., Bumbac, G., Plesu, V., Muja, I. Popescu, C.D., Modelling and Simulation of Kinetics
and Operation for the TAME Synthesis by Catalytic Distillation, 1999;
Gr. Bozga, G. Bumbac, V. Plesu, I. Muja, D. C. Popescu, Modelling and Simulation of Kinetics
and Operation for the TAME Synthesis by Catalytic Distillation, European Symposium on
Computer Aided Process Engineering – 13, pp. 575- 580, 2003;
Bumbac, G., Bozga, G., Toma, A., Ion, I., Simion, C, Kinetic studies on the etherification of c5-
alkenes to fuel ether TAEE, Proceedings of 33rd International Conference of SSCHE, 2006;
Doherty M. F. and M. F. Malone, Conceptual Design of Distillation Systems, McGraw Hill,
2001;
Roemer, M. H. and Durbin L. D., Ind. Engng. Chem., Fundls., 6, 120, 1967.

Acknowledgment

We acknowledge the financial support of the European Commission within the 6 th Framework
Program, Project “INSERT – Integrating Separation and Reaction Technologies”: Contract-No:
NMP2-CT-2003-505862