Afra Alethiana

16/398534/PA/17495

Journal Review
Acid-Catalyzed Cracking of Paraffinic Hydrocarbons.
1. Discussion of Existing Mechanisms and Proposal of a New Mechanism

The generally accepted theory of acid-catalyzed cracking of paraffinic hydrocarbons is a carbenium

ion mechanism according to which a classical carbenium ion is formed from a hydrocarbon, which then
undergoes B-scission to give a carbenium ion of lower carbon number and an olefin. It is shown that this
theory fails to provide a satisfactory explanation for certain characteristic features of catalytic cracking and
hydrocracking. A new mechanism is now proposed which is the catalyzed isomerization of paraffin, viz.,
The intermediate of a nonclassical carbonium ion of the cyclopropyl structure. This new theory provides
an explanation for many of the characteristics of cracking processes.

The main difference is that the intermediate of a nonclassical carbonium ion instead of a classical
carbenium ion is postulated, very much in the same way as in the skeletal isomerization of paraffin. It
involves the intermediacy of carbonium ions of a nonclassical type, viz., the protonated cyclopropane
structure. Isomerization of the carbon chain occurs by breakage of either of the two bonds linking the
bridged methylene group with the carbon atoms of the main chain.

Breakage of the other two bonds of the cyclopropane ring is possible, but will in this case result in
a secondary carbenium ion with a straight chain. This will lead to either the original butane molecule or a
n-butane molecule in which two carbon atoms have exchanged their position in the chain. If the
intermediacy of a nonclassical carbonium ion as opposed to a classical carbenium ion in isomerization is
accepted, there is no reason why this nonclassical ion should not play a role in cracking as well.

It is likely that the activation energy for the reaction pathway that leads to cracking is higher than
the one which leads to isomerization from the common intermediate. This means that higher temperatures
will favor cracking more than isomerization. Catalysts of very high acidity which can catalyze the
carbenium ion reactions at low temperature therefore seems to offer the best prospects for maximizing the
selectivity in the isomerization of paraffins.

A new mechanism has been proposed which assumes a protonated cyclopropane as a reaction inter-
mediate, just as in the mechanism of isomerization of paraffin. This new mechanism not only cast a anew
light on the relation between hydro isomerization and hydro- cracking, but it is also capable of providing a
logical explanation for many experimental facts which have hitherto not been explained in a satisfactory
way, such as the low formation of C1and C2, the strong branching in the cracked paraffin fractions, and the
strong increase of cracking reactivity with carbon numbers above 7. A more detailed and more quantitative
interpretation of experimental result obtained in catalytic cracking as well as hydrocracking by the new
mechanism will be presented in the following papers of this series.

Sie, S.T., 1992, Acid-Catalyzed Cracking of Paraffinic Hydrocarbons, Discussion of Existing Mechanisms
and Proposal of a New Mechanism, Ind. Eng. Chem. Res, 31, Koninklijke/Shell Laboratorium,
Amsterdam (Shell Research B.V.), P.O. Box 3003, 1003 AA Amsterdam, The Netherlands, p1881-
1889.
 Journal Review
Acid-Catalyzed Cracking of Paraffinic Hydrocarbons.
2. Evidence for the Protonated Cyclopropane Mechanism from Catalytic Cracking Experiments

Experimental results obtained in studies on catalytic cracking of normal paraffins as described in

the literature are interpreted in terms of the protonated cyclopropane mechanism described in the previous
paper of this series. It is shown that this mechanism is capable of explaining the observed sharp increase in
reaction rate with increasing carbon number of normal paraffins above C7 in catalytic cracking.

The correspondence is sufficiently good to serve as supporting evidence for the new mechanism.
A closer correspondence can hardly be expected because of the simplifying assumption made, and the
possibility that some pre-isomerization has affected the observed cracking rates supposed to be attributable
to cracking of normal paraffins only. In addition, some differences in carbon level on the catalyst as well
as adsorption of the heavier hydrocarbons may have played a role.

Under the usual conditions of catalytic cracking secondary cracking of the cracked fragments
generally takes place and this will mostly affect the concentration of the heavier fragments, in view of the
dependence of crack ability on the length of the carbon chain.

Another argument against consecutive isomerization being the only source of branched paraffins
can be derived from cracking experiments with n-hexadecane over silica alumina and silica magnesia
catalysts at different degrees of conversions. The presently proposed mechanism will lead to 2-
methylalkanes as predominant paraffinic fragments (cf. Scheme I). Examination of detailed product
compositions obtained by cracking n-dodecane over various catalysts indeed shows that the 2-methyl
isomers are the most abundant isomers among the C6 and C7 paraffins.

Notwithstanding the fact that the composition of a practical feedstock is quite complex and
molecular structures are less well defined than the pure normal paraffins discussed above, the characteristics
of the cracked products predicted by the protonated cyclopropane mechanism are well recognizable in
actual catalytic cracking processes.

The expected predominance of the iso structures in the saturated products of catalytic cracking is
not restricted to butanes and pentanes; it can also be found in higher fractions. In catalytic cracking
experiments with different catalysts Magnussen and Pudas reported 4-5 times higher yields of isoheptanes
than of n-heptane.

The proposed new mechanism for acid-catalyzed cracking of paraffinic hydrocarbons, which
assumes a protonated dialkyl cyclopropane as a reaction intermediate, is in good agreement with many
characteristic features of catalytic cracking as observed experimentally. The mechanism predicts that CS
should be largely propene, and that the saturated hydrocarbons should be characterized by a high degree of
branching, in contrast to the olefins, which should be predominantly linear.

Sie, S.T., 1993, Acid-Catalyzed Cracking of Paraffinic Hydrocarbons, Discussion of Existing Mechanisms
and Proposal of a New Mechanism, Ind. Eng. Chem. Res, 32, Koninklijke/Shell Laboratorium,
Amsterdam (Shell Research B.V.), P.O. Box 3003, 1003 AA Amsterdam, The Netherlands, p397-
402.