Catalytic reforming

Catalytic reforming is a chemical process used to convert petroleum refinery naphthas, typically having
low octane ratings, into high-octane liquid products called reformates which are components of high-
octane gasoline (also known as petrol). Basically, the process re-arranges or re-structures
the hydrocarbon molecules in the naphtha feedstocks as well as breaking some of the molecules into
smaller molecules. The overall effect is that the product reformate contains hydrocarbons with more
complex molecular shapes having higher octane values than the hydrocarbons in the naphtha
feedstock. In so doing, the process separates hydrogen atoms from the hydrocarbon molecules and
produces very significant amounts of byproduct hydrogen gas for use in a number of the other
processes involved in a modern petroleum refinery. Other byproducts are small amounts
of methane, ethane, propane and butanes.

This process is quite different from and not to be confused with the catalytic steam reforming process
used industrially to produce various products such as hydrogen, ammonia and methanol from natural
gas, naphtha or other petroleum-derived feedstocks. Nor is this process to be confused with various
other catalytic reforming processes that use methanol or biomass-derived feedstocks to produce
hydrogen for fuel cells or other uses.

HISTORY
In the 1940s, Vladimir Haensel,[1] a research chemist working for Universal Oil Products (UOP),
developed a catalytic reforming process using a catalyst containing platinum. Haensel's process
was subsequently commercialized by UOP in 1949 for producing a high octane gasoline from low
octane naphthas and the UOP process become known as the Platforming process.[2] The first
Platforming unit was built in 1949 at the refinery of the Old Dutch Refining Company
in Muskegon, Michigan.

In the years since then, many other versions of the process have been developed by some of the
major oil companies and other organizations. Today, the large majority of gasoline produced
worldwide is derived from the catalytic reforming process.

To name a few of the other catalytic reforming versions that were developed, all of which utilized
a platinum and/or a rhenium catalyst:

 Rheniforming: Developed by Chevron Oil Company.

 Powerforming: Developed by Esso Oil Company, now known as ExxonMobil.
 Magnaforming: Developed by Englehard Catalyst Company and Atlantic Richfield Oil
Company.

Reforming to increase the octane rating of heavy gasoline components. Although this
process is very effective in improving the octane rating of heavy gasoline components, it
does so by increasing the aromatic content of the fuel. Since reformulated gasoline now
limits the maximum aromatic content in gasoline, the Refinery can no longer produce the
necessary octane rating for its gasoline products solely by use of its existing Catalytic
Reforming process.

Catalysts and Catalysis

A Catalyst is a substance that affects the rate
of chemical reaction but emerges from the
process unchanged.
Catalysis is the occurrence, study, and use of
catalysts and catalytic processes.
Normal Pentane Octane Number = 62

Iso-Pentane Octane Number = 95

Gasoline has a number of specifications that must be satisfied to provide high performance for
today's motor vehicles. Octane, however, is the most widely recognized specification. The octane
number is generally reported as the average of Research Octane Number (RON) and Motor
Octane Number (MON), (R+M)/2. MON is the more severe test, so for a given fuel RON is always
higher than MON.
Unfortunately, heavy naphtha from atmospheric distillation, which forms a significant
percentage of the gasoline blend, has an octane rating of around 50 (R+M)/2. Octane
demand for gasoline ranges from upper-80 to mid 90 (R+M)/2. Catalytic Reforming is
the workhorse for octane upgrade in today's modern refinery. Molecules are reformed
into structures that increase the percentage of high octane components while reducing the
percentage of low octane components.

The dehydrocyclization and dehydrogenation reactions are desired because

they produce hydrogen. Hydrocracking and hydrodealkylation are mostly

undesired reactions because they lower the reformate and hydrogen yields,

while coke formation deactivates the catalyst and reduces the cycle length. The

dehydrogenation of cyclohexanes to aromatics is very selective and nearly

complete, the reactions involving paraffins and alkylcyclopentanes are most

critical for good reformate yield during high-severity reforming . High

octane numbers can only be achieved through extensive paraffin

dehydrocyclization, as the octane number obtained from dehydrogenation of

naphthenes and from isomerization of paraffins is well below the desired values

. Paraffin dehydrocyclization is relatively slow compared to paraffin

hydrocracking under normal reformer conditions.

High temperature and low pressure favor the thermodynamic feasibility and

selectivity of the three most important reactions: dehydrogenation of

cyclohexanes, dehydroisomerization of cyclopentanes, and dehydrocyclization

of paraffins. For the other reactions - isomerization, hydrocracking and

hydrogenolysis - temperature and pressure only slightly influenced by

equilibrium limitations. Generally, high temperature and low pressures would

seem most desirable, but deactivation of the catalyst and hydrocracking and

hydrogenolysis reactions prevail. For this reason, the process conditions are a

compromise. The three most important reactions are endothermic and dominate

the heat balance, producing a decrease in temperature along the catalyst bed.

Only in the last reactor, where the slowest reactions occur, is the endothermicity

of the partial dehydrocyclization of paraffins is balanced by the exothermicity

of hydrocracking and hydrogenolysis reactions. Only these last two molecule-

rupture reactions consume hydrogen, however the process is a net hydrogen

producer.