A single-event microkinetic model for xylene isomerisation and

ethylbenzene dealkylation

K. Toch, J. W. Thybaut, B. Vandegehuchte, G. B. Marin

Ghent University, Laboratory for Chemical Technology, Krijgslaan 281-S5, 9000 Ghent,
Belgium; tel. +32 9 264 55 63, e-mail: Joris.Thybaut@UGent.be

Xylenes are very important petrochemical products that are encountered in the
production of phtalic acid anhydride (from o-xylene) and terephtalic acid (from p-xylene) [1].
Especially the latter component is of high industrial relevance since it is an intermediate in the
production of polyethylene terephtalate (PET). Because the amounts in which the three xylene
isomers are obtained from, e.g., catalytic reforming, thermal cracking, cokes oven effluent
gases,... are not matching with the market demand, processes have been developed to convert
the less desired isomer, i.e., m-xylene, into the more commercially interesting o-xylene and,
mainly, p-xylene. Inevitably, also some ethylbenzene is contained in the xylenes mixture and,
hence, ethylbenzene dealkylation occurs during the xylene isomerisation.
As part of this work a fundamental Single-Event MicroKinetic (SEMK) model for xylene
isomerisation and ethylbenzene dealkylation has been constructed. It accounts for all
elementary steps occurring in the reaction network, see Figure 1, i.e., physisorption of the
reactants into the zeolite pores, 78 (de)-protonation, 24 1-2 methyl shift, 16 exocyclic β-
scission, and 113 transalkylation reactions at the acid sites and 18 aromatic hydrogenation on
the metal sites between 18 aromatic components, 18 cycloalkanes, 78 aromatic carbenium
ions and 1 alkane. The corresponding reaction network has been generated using an
automated reaction network generation program.
The model has been tested against an experimental data set on a Pt/H-ZSM5 zeolite. The
temperature was varied between 350 to 400°C, the total pressure ranged from 0.4 to 1.2 MPa,
and the hydrogen to hydrocarbon ratio was between 1 and 5. One activation energy per
reaction family was obtained by regression for the 1-2 methyl shift, exocyclic β-scission,
CH3 CH3

CH3 H3C
CH3

CH3 CH3
Physisorption

Physisorption Zeolite
CH3
CH3

Metal sites CH3 Acid sites

CH3 Methylshift
CH3
+
CH3 CH3 (de-)Protonation
CH3

Chemisorption (de-)Protonation CH3

(de-)Hydrogenation
+
CH3
CH3 CH3 CH3
CH3 CH3
CH3
CH3
+
CH3
Chemisorption H3C CH3 CH3
+
+
CH3
Transalkylation Dealkylation
CH3 (de-)Protonation

CH3

H3C CH3

Physisorption
CH3 Physisorption
CH3 CH3
CH3 H3C CH3 C 2H 6

Figure 1: Reaction network considered in xylene isomerisation and ethylbenzene

dealkylation
 Table 1: Assumed variation in degrees of freedom and estimated activation
energies/reaction enthalpies for the considered reaction families
variation in degrees Activation
of freedom Energy/Reaction
Enthalpy (kJ mol-1)
protonation loss of all -136.30 ± 0.27
translational freedom
methyl shift no changes 114.03 ± 0.62
β-scission gain of 1 translational 173.60 ± 0.12
degree of freedom
transalkylat loss of 1 translational 133.27 ± 0.37
ion degree of freedom
hydrogenat loss of 1 translational 74.57 ± 0.45
ion degree of freedom

Figure 2: Parity diagrams for ethylbenzene conversion (left) and xylene losses
transalkylation and hydrogenation reactions, while quasi equilibrium was assumed for
(de)-protonation leading to a reaction enthalpy to be estimated. The corresponding
preexponential factors were obtained by considering the changes involved in degrees of
freedom between the reactant(s) and the species in the transition state or the reaction product,
see Table 1. The parameter values related to physisorption in the zeolite pores and chemical
adsorption on the Pt sites were taken from the literature [2-3].
Figure 2 illustrates the model’s adequacy in reproducing the main experimental
responses, i.e., the ethylbenzene conversion, mainly by dealkylation (exocyclic β-scission)
into benzene and ethane, and the xylene losses by disproportionation (transalkylation)
reactions. The model parameters are in line with literature reported values [4]: from the acid
catalyzed reactions, methyl shifts have the lowest activation energy while exocyclic β-scission
has the highest. The protonation enthalpy obtained indicates a strong chemisorption of the
aromatic reactants on the acid sites compared to that of alkenes on a reference USY zeolite.
In this work, the SEMK methodology has been applied for the first time to xylene
isomerisation and ethylbenzene dealkylation. Only minor modifications related to the new
reaction families encountered needed to be accounted for the available reaction network
generation and regression tools to come to an adequate simulation of the main and the minor
responses. It illustrates the versatility of the method in the assessment of catalytic kinetics.
References
[1] Chen, N.Y., Ind. Eng. Chem. Res., 2001. 40(20) 4157.
[2] Thybaut, J.W., M. Saeys, and G.B. Marin, Chem. Eng. J., 2002. 90(1-2) 117.
[3] Reshetnikov, S. I., S. B. Ilyin, A.A. Ivanov, and A. S. Kharitonov, React. Kinet.
Catal. Lett., 2004. 83(1) 157.
[4] Thybaut, J. W., G. B. Marin, G. V. Baron, P. A. Jacobs, and J. A. Martens, J. Catal.,
2001. 202(2) 324.