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Reaction Principle 3
Reaction Principle 3
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.
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.
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.
Naphthene
Very fast
dehydrogenation
Paraffin isomerization
Fast
Slow
Very fast
Endothermic
Not reached
Very slow
Exothermic
Not reached
Paraffin
dehydrocyclization
Paraffin
dehydrogenation
Hydrocracking