-

The quantity of commercially available toluene exceeded its demand as raw material,
thus the price of the toluene is lower than benzene and xylene.
The choice of a particular method of disposal is strongly influenced by the prevailing
prices of benzene, toluene and xylenes.
(a) When the prices of both benzene and xylenes are low, it may be more economical to
dispose of the toluene by blending it into gasoline.
(b) If the price of benzene is high in comparison with that of toluene and xylenes,
hydrodealkylation may be the most economical process.

Hydrodealkylation
(a) produces benzene and methane (worthless compored to TB), it is more sensitive to changes in
feedstock and product price.
(b) uses up hydrogen. When hydrogen is not readily available, its price may adversely affect the
profitability of hydrodealkylation.
Disproportionation
For vapor phase, Hydrogen (as a diluents gas) is used in disproportionation in order to prevent
coke deposition (by cracking rxn) and thus catalyst deactivation, it is not consumed and can be
recycled.
(a) Catalyst liquid phase: metal halides (Friedel-Crafts catalysts)
Vapor phase: solid catalysts (Silica-alumina & zeolites modernite / faujaasite)
- Modernite - (adv) highest activity for this rxn
(dis) low selectivity, low stability (coke formation is so fast that the activity
decreases to a low value in a short time)
- Thus, use of composite catalysts: modernite-aluminium fluoride etc

It is assumed that toluene is the only methylbenzene presents in the above rxns as the conc. of
the toluene is higher than the other aromatic species present (eg similar rxns are possible with
benzene, xylene, trimethylbenzene etc formed)
-

Stability diagram to det the relative importance of the rxns

Cal. The eq. conversion of disproportionation as a f(T)
Heat effect of rxn
Toluene conversion
Selectivity of disproportionation
Yield of disproportionation products

1. for disproportionation, the change in free enthalpy is slightly positive, the conversion is not
complete (high conversion is improbable & selectivity is small), thus a catalyst is needed which
will selectively accelerate the rxn rate of disproportionation where all the rxn proceed at the same
rate.
2. rxn 5 results in coke formation (can be neglected for slow deactivation of catalysts 30% in
3000hrs, max. carbon content of the catalyst is 4.5% at 500C)
3. ring hydrogenation is not detected, so rxn 6 can be neglected
4. from methyl group balance, all CH4 can be accounted for the hydrodealkylation, so rxn 4 can
be neglected.

Rxn 1-11 are disproportionation, isomerization and transalkyation (heat effect is small, thus the
eq conversion and product distribution is independent on T- in line with Table 2-4)
Rxn 12-15 are hydrodealkylation of toluene, hydro-cracking of toluene to methane and thermal
cracking of toluene to carbon and hydrogen, and the hydrogenation of toluene to
methylcyclohexane (EXOTHERMIC)

Yield, Selectivity and Conversion

Only rxns 1,2 and 3 are considered, since the feed consists of toluene and H2, the yield of
xylenes and trimethylbenzenes are very small compared to the conc of toluene (thus rxn 4 to 6
can be neglected)

(1) the liquid phase rxn catalysed by halides has very low selectivity towards toluene
disproportionation, reasons:
1. higher stability and basicity of m-xylenes relative to o- and p-xylene
2. faster rate of isomerization fo both o- and p- xylene to m-xylene than that of m-xylene to
other isomers
3. the

-complexes btw m-xylene and halide catalysts are more stable than those of the

isomers at low T
--- at higher T, enough energy is able to make the sigma complexes less stable and cause mxylene to undergo isomerization as well as disproportionation & transalkylation.
(2) the gas phase rxn, zeolites makes better disproportionation catalysts (higher activity)
1. modernite and faujasite suffer from a rapid loss of activity
2. best activation T is 500C (where the selectivity increase with T)
> 500C, the catalysts performance deteriorate (destruction of crystalline structure of the catalyst
by such a high T / by a change in the nature of the active site
such as by transformation of the sites from Bronsted acid types, which are considered responsible
for this type of reaction into Lewis acid types which are believed to be inactive.
** by dehydration rather than destruction of the structure of zeolites
*** since rehydrating the catalyst after activation at 550C restored its TD activity & the specific
surface area of catalyst didnt change
72 w% HY zeolite, 18 w% B-AIF3 and 10 w% Cu has the most satisfactory overall activity,
selectivity and stability of the catalysts tested. While this catalyst is less active than HY zeolite,
its selectivity and stability are much higher.
The acidic properties of the zeolite-based catalyst are consistent with the hypothesis that its high
performance for the disproportionation of toluene is due to its acidity.

Thehydrogen/tolueneratioiskeptconstantat16.7mol/mol.

Conclusion
High total P, high hydrogen/toluene ratio, high P hydrogen reduce deactivation of catalyst
The following need to be specified when designing the reactor:
reactor type, reactor inlet temperature and pressure, toluene flow rate and hydrogen/toluene ratio
(T,P,F and R, respectively) as well as r, the reaction rate equation, the required conversion,
catalyst particle dimensions and the mode of operation of the reactor, that is, whether adiabatic,
isothermal or otherwise.
Industrial toluene disproportionation processes employ total pressures of 30 ata and higher (cf.
chapter 1). Presumably this may be partly due to the fact that for these processes a high hydrogen
partial pressure is needed to maintain the catalyst at a reasonably stable level of activity. (using
industrial catalysts: natural modernite treated with HCl)