CHEMICAL REACTIONS IN ISOMERISATION PROCESS

Catalyst activity, selectivity, stability The main characteristics of a catalyst other than its physical and mechanical properties are:

The activity which is the catalyst ability to increase the rate of the reactions involved. It is measured by the temperature at which the catalyst must be operated to produce a product on-specification, for a given feed, all other operating conditions being equal. The selectivity expresses the catalyst ability to favour desirable reactions rather than others. The stability characterizes the change with time of the catalyst performance i. e., activity, and selectivity! when operating conditions and feed are stable. It is chiefly the polymers or co"e deposit which affects stability, because it decreases the metal contact area. Traces of metal in the feed also adversely affect stability.

Chemical Reactions The reactions are carried out in two steps : #st step : $ydrogenation of benzene. %nd step : Isomerization of normal paraffins Hydro enation o! "en#ene &enzene hydrogenation is according to the reaction :

0 *$%

)yclohexane!

This reaction is highly exothermic and occurs in a separate reactor, namely the &enzene 'aturation (eactor. This allows to carry out the isomerization reactions separately at lower temperatures in the downstream isomerization reactors. Isomeri#ation Isomerization is the conversion or rearrangement of the structure of a compound to its more branched, higher octane structure. These rearrangements are depicted by the following formula:

)$* )$* - )$% - )$% - )$% - )$* n-pentane (+, - .%!

)$* - )$ - )$% - )$* isopentane

(+, - /*!

)$* - )$% - )$% - )$% - )$% - )$* n-hexane (+, - *1!

)$* - )$ - )$% - )$% - )$* )$* % methylpentane (+, - 23 !

)$* - )$% - )$ - )$% - )$*

)$* * methylpentane (+, - 24 ! )$*

)$* - ) - )$% - )$*

)$* %,% dimethylbutane (+, - /%! )$*

)$* - )$ - )$ - )$*
)$* %,* dimethylbutane (+, - #13!

These reactions, as shown, are reversible and the final distribution of the isomers is based on the equilibrium composition which is dictated by the reactor process conditions and "inetics. In addition to the isomerization reactions, there are other side reactions ta"ing place as well, and some of them are not desirable.

Na$hthenes Rin O$enin The three naphthenes which are typically present in an isomerization feed are cyclopentane )5!, methyl cyclopentane 6)5! and cyclohexane )$!. These naphthenic rings brea" and hydrogenate to form paraffins. (ing opening reactions increase with increasing temperature and again are governed by equilibrium compositions at the reactor process conditions. 7t typical isomerization reactor conditions the conversion of naphthene rings to paraffins will be approximately %1-*1 percent.

0 $% )4$#1 cyclopentane!

)4 $#%

0 $%

). $#3

).$#% cyclohexane! )$*

0 $% ).$#% methyl cyclopentane!

). $#3

,aphthenic or cyclic components tend to inhibit the isomerization reactions and are therefore undesirable in large quantities. The cyclic components are absorbed on the catalyst and reduce the active sites available for paraffin isomerization. They also consume hydrogen, produce exothermic heat which is undesirable from the isomerization equilibrium standpoint. $owever undesirable as they are, they are a natural fraction of )48). cut naphtha and are difficult to eliminate without also eliminating other desirable components.

Hydrocrac%in +perating at the low severity reactor conditions, very little ) 48). hydrocrac"ing occurs in the isomerization reactors. )2 paraffins however hydrocrac" readily to produce )* and )3 components. 6uch of the hydrocrac"ing occurs in the first reactor which typically operates at a higher temperature. $ydrocrac"ing reactions consume hydrogen, and hence it is recommended to restrict the )20 content of the isomerization feedstoc". )2 $#. 0 $% )* $9 0 )3 $#1

Catalyst Catalyst Mechanisms There are several reaction mechanism theories presented based on the type of catalyst used, i.e. whether it is a dual functional catalyst consisting of a metal and a support or if its acidity is enhanced by a halogen. :hatever the type of catalyst used the intermediate step is the same i.e., the formation of a carbonium ion or carbocation. Isomerization on dual-function catalysts in a hydrogen atmosphere is generally described by the following reaction scheme: 5t )$* - )$% - )$% - )$% - )$*

)$* - )$% - )$% - )$ - )$% 0 $%

The metallic function of the catalyst, in this case platinum, catalyses the formation of an olefin intermediate by dehydrogenation of the paraffin. The olefins are then converted into carbonium ions by the addition of a proton during adsorption onto the acidic surface of the catalyst. )$ )$ )$ )$ - )$* * % % ) 3 )$* - )$% - ) - )$* 0$0

)$* - )$% - )$% - )$ - )$% '"eletal rearrangement then occurs : )$* - )$% - )$% - )$ - )$*

The rearranged carbonium ion is then desorbed as an iso-olefin which is then hydrogenated by the catalyst metallic function to the iso-paraffin : ) 3 ) 3

)$* - )$% - ) - )$* )$* - )$% - ) - )$% 0 $+

) 3 5t )$* - )$% - ) - )$% 0 $% )$* - )$% - )$ - )$* ;ual-functional hydro-isomerization catalysts which operate at very low temperature have stronger acid sites than those which require higher temperatures. In this case, the theory postulates that the carbonium ion is formed by direct hydride ion abstraction from the paraffin by the acid function of the catalyst. ) 3

)$* - )$% - )$% - )$% - )$* 0 $+ 7 )$* - )$ - )$% - )$% - )$* 0 $% 0 7 7fter rearrangement, isopentane is formed and the chain is propagated by the generation of a new acid site. )$* )$* - ) - )$% - )$* 0 7 0 $% )$* )$* - )$ - )$% - )$* 0 $ + 7

7nother principal theory of initiation and propagation is that based on the <riedel-)rafts theory. <riedel-)rafts isomerization is believed to require the presence of traces of olefins or al"yl halides as carbonium ion initiators with the reaction thereafter proceeding through chain propagation. The initiator ion, which needs to be present only in small amounts may be formed by the addition of $)l to an olefin which is present as an impurity in the paraffin or is formed by paraffin hydrocrac"ing. ()$ - )$% 0 $)l ( )$ )$* 0 )l

The initiator then forms a carbonium ion with the paraffin to be isomerized.
( )$ )$* 0 )$* - )$% - )$% - )$% - )$*

( )$% )$* 0 )$* - )$ - )$% - )$% - )$*

7fter s"eletal rearrangement, isopentane is formed and the chain is propagated by the generation of a new normal carbonium ion. ) 3 ) 3 )$*-)-)$%-)$* 0 )$*-)$%-)$%-)$%-)$* )$*-)$-)$%-)$* 0 )$*-)$-)$%-)$%-)$*