By Ganzwa Bernard Gumbo harvey

The aim of this process is to improve the octane number of a naphtha feedstock by changing its chemical composition. Catalytic reforming is considered the key process for obtaining benzene, toluene, and xylenes (BTX). These aromatics are important intermediates for the production of many chemicals

Hydrocarbon compounds differ greatly in their octane ratings due to differences in structure. In general, aromatics have higher octane ratings than paraffins and cycloparaffins Increasing the octane number of a low-octane naphtha fraction is achieved by changing the molecular structure of the low octane number components

The feed to a catalytic reformer is normally a heavy naphtha fraction produced from atmospheric distillation units. The naphtha must be hydro treated to saturate the olefins and to hydrodesulfurize and hydrodenitrogenate sulfur and nitrogen compounds. Olefinic compounds are undesirable because they are precursors for coke, which deactivates the catalyst. Sulfur and nitrogen compounds poison the reforming catalyst.

Feeds with a high naphthene content are easier to aromatize than feeds with a high ratio of paraffins Feeds with higher end points (200C) are favorable because some of the long-chain molecules are hydrocracked to molecules in the gasoline range

The catalysts generally used in catalytic reforming are dual functional to provide two types of catalytic sites, hydrogenation-dehydrogenation sites and acid sites. The former sites are provided by platinum and the latter is provided by an alumina carrier. The two types of sites are necessary for aromatization and isomerization reactions.

Bimetallic catalysts such as Pt/Re have better stability, increased catalyst activity, and selectivity. Trimetallic catalysts of noble metal alloys are also used. These catalysts can tolerate higher sulfer naphtha feeds (>1 ppm)

Many reactions occurs in the reactors. aromatization reactions, which produce aromatics. Isomerization reactions, which produce branched paraffins. Hydrocracking and hydrodealkylation reactions, these are not directly involved in aromatics formation.

The two reactions directly responsible for enriching naphtha with aromatics are:dehydrogenation of naphthenes

1.

2. the dehydrocyclization of paraffins to aromatics

Carbocation formation may occur by abstraction of a hydride ion from any position along the hydrocarbon chain. Cyclization of 1-heptene over the alumina catalyst can occur by the following successive steps:

Isomerization reactions may occur on the platinum catalyst surface or on the acid catalyst sites Most isomerization reactions, however, occur through formation of a carbocation. The formed carbocation could rearrange through a hydride-methide shift that would lead to branched isomers

Example: the isomerization of n-heptane to 2methylhexane through 1,2-methide hydride shifts

Isomerization of alkylcyclopentanes may also occur on the platinum catalyst surface or on the silica/alumina.

Hydrocracking is a hydrogen-consuming reaction that leads to higher gas production and lower liquid yield. hydrocracking long-chain molecules can produce C , C , and C hydrocarbons that are suitable for hydrodecyclization to aromatics.
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Hydrodealkylation is a cracking reaction of an aromatic side chain in presence of hydrogen This reaction is particularly important for increasing benzene yield when methylbenzenes and ethylbenzene are dealkylated

Hydrodealkylation may be represented by the reaction of toluene and hydrogen.

Catalytic reformers are normally designed to have a series of catalyst beds (typically three beds). The first bed usually contains less catalyst than the other beds. The second and third reactors contain more catalyst than the first one to enhance the slow reactions and allow more time in favor of a higher yield of aromatics and branched paraffins

the reactor outlet temperature is lower than the inlet temperature. The effluent from the first and second reactors are reheated to compensate for the heat loss. Normally, catalytic reformers operate at approximately 500525C and 100300 psig, and a liquid hourly space velocity range of 24/ hr.

LHSV is an important operation parameter expressed as the volume of hydrocarbon feed per hour per unit volume of the catalyst. Products from catalytic reformers (the reformate) is a mixture of aromatics, paraffins and cycloparaffins ranging from C -C . The mixture has a high octane rating due to presence of a high percentage of aromatics and branched paraffins
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Extraction of the mixture with a suitable solvent produces an aromatic-rich extract, which is further fractionated to separate the BTX components Regeneration of the catalyst may be continuous for certain processes In many processes, regeneration occurs by shutting down the unit and regenerating the catalyst (Semi-regenerative)

A typical reformer feed derived from Middle East crude contains about 65% wt. paraffins, 20% wt. naphthenes and 15% wt. aromatics. After processing, the analysis is about 45% wt. paraffins1, virtually no naphthenes and 55% wt. aromatics. The octane number of the reformer feed is about 50, while the octane number of the product is about 100. The product from the separator contains light gases from partial cracking, and these are removed by fractional distillation.