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Reaction principle

During catalytic reforming, gasoline fractions obtained from the distillation of crude oil are being
passed at ca.500 - 550C over beds of previously chlorinated platinum catalysts on fixed porous
aluminum. Therefore, the process is also called plate-reforming. Three processes mainly increase
the octane number.

Fig.3
Isomerisation of long-chain to branched alkanes

Fig.4
Dehydrogenation of cycloalkanes to aromatic compounds

Fig.5
Dehydrocyclization of long-chain alkanes to aromatic compounds
Fragmentation into shorter alkanes (cracking) and dehydrogenation to olefins are side reactions
observed during catalytic reforming. The formation of olefins, especially of polyolefins, is
undesirable because they reduce the stability of fuels towards oxidation and have a tendency to
polymerize. The formation of undesirable olefinic compounds is prevented by adding hydrogen
to the mixture of alkanes thereby re-hydrogenating the olefins to the corresponding alkanes. The
activity of the Pt-catalyst is insufficient for hydrogenation to the desired anti-knocking aromatic
compounds.

Fundamentals of Catalytic Reforming


Chemistry
A large number of reactions occur in catalytic reforming over bifunctional catalysts, such as
dehydrogenation and dehydroisomerization of naphthenes to aromatics, dehydrogenation of
paraffins to olefins, dehydrocyclization of paraffins and olefins to aromatics, isomerization or
hydroisomerization to isoparaffins, isomerization of alkylcyclopentanes and substituted

aromatics, and hydrocracking of paraffins and naphthenes to lower hydrocarbons. All reactions
are desirable except hydrocracking, which occurs to a greater extent at high temperature and
converts valuable C+ molecules (reformate) into light gases. Some examples of these reactions
are shown in Figure 4.2 Most commonly, the reactions occurring during catalytic reforming are
classified into the following four types.

Figure 4.2. Examples of catalytic reforming reactions.

Thermodynamics
The most rapid reactions (i.e., dehydrogenation of naphthenes) reach thermo-dynamic
equilibrium, while the others are controlled by kinetics. Increasing the reaction temperature and
lowering the pressure have both a positive effect on the reaction rate and thermodynamic
feasibility as to the dehydrogenation of naphthenes (the most important reaction in catalytic
reforming). The effect of these variables on thermodynamic equilibrium for the other reactions is
slighter.
Table 4.2 summarizes the thermodynamic effect of the main reforming reactions. Other
effects are the following:
The dehydrogenation of naphthenes and paraffins is rapid and equilibrium concentrations are
established in the initial portions of a catalyst bed.
Olefins are readily hydrogenated, and at equilibrium only small concentrations can exist.

The isomerization of paraffins is a sufficiently rapid reaction and primarily thermodynamically


controlled, which means that actual concentrations are near equilibrium.
The dehydrocyclization of paraffins is a much slower reaction and kineti-cally controlled.
Hydrocracking rates increase with pressure and lower the reformate yield.
Coking is very slow but increases rapidly at low hydrogen pressure and high temperature.
Thus, it is highly desired to operate reactors at high temperature and low pressure; however,
catalyst deactivation due to coke deposition is also favored at those conditions. In addition,
lowering hydrogen partial pressure results in an increase in the aromatization rate and a decrease
in the rate of hydrocracking.
TABLE 4.2. General Thermodynamic Comparison of the Major Catalytic Reforming
Reactions

Rate of Reaction Heat of Reaction Thermodynamic Equilibrium

Naphthene
Very fast

Very endothermic Reached

dehydrogenation

Naphthene isomerization Fast

Mildly exothermic Reached

Paraffin isomerization

Fast

Mildly exothermic Reached

Slow

Very endothermic Not reached

Very fast

Endothermic

Not reached

Very slow

Exothermic

Not reached

Paraffin
dehydrocyclization

Paraffin
dehydrogenation

Hydrocracking