Fuel Technology-Ι

(ENT-332)
Secondary Processing of crude Oil
Reforming of Naphtha : This refinery process is used to upgrade low
octane naphtha to high octane motor fuel, which after reforming is
termed as ‘reformate’. The hydrocarbons content of naptha are paraffins,
naphthenes and aromatics in C5 to C12 range. This process involves the
reconstruction of naphtha constituent of hydrocarbon molecules without
changing the boiling range. Naphtha obtained from catalytic or thermal
cracking operation contains some olefins also. The reformed naphtha or
reformate is rich in aromatics and isoparaffins. Hydrogen is produced in
this process which is used in hydroprocessing of different cuts in the
refinery. Reforming is accomplished by processing the naphtha feed at
elevated temperature (930-1000F) and moderate pressure (4-30 bar) in
presence of hydrogen. Catalyst used is mainly platinum based.
 Reforming of Naphtha
The chloride treated alumina is used as support to improve acidic
sites of the catalyst. The reforming unit practiced in the refinery
are of two types, one is semi regenerative reforming, where the
catalysts are regenerated in a cycle of 1 to 2 years and another
type is continuous regeneration type, where each catalysts
particles has a cycle time of typically 6 to 8 days between
regenerations. UOP (Universal Oil Product) first commercialized
the reforming process in the year 1949, who coined the process
as ‘Platforming’, after the name of the platinum catalyst used by
them. They also developed the continuous catalyst regeneration
(CCR) system in the operation and this system alongwith catalyst
modification can upgrade naphtha upto 108 octane number.
 Reaction Chemistry of Reforming
Four major reactions of paraffin's and naphthenes occur in this process. These
are;
1) Dehydrogenation of naphthenes Dehydrogenation of naphthenes to the
corresponding aromatics is a fast process. It is endothermic reaction and
favored by high temperature and low pressure. One example of this reaction is
the conversion of a naphthene, methyl cyclohexane to toluene. This reaction
releases three moles of hydrogen per mole of naphthene and up gradation of
octane number of more than 25 units.
2) Isomerisation of naphthenes and paraffin's An example of isomerisation of
naphthenes is conversion of alkyl cyclopentane to cyclohexane. Aromatisation
of cyclohexane is the next step which improves the octane number.
Isomerisation of naphthene involves ring opening and ring rearrangement.
Isomerisation of paraffin's produce isoparaffins from normal paraffin, thereby
increases octane number, for example, when n-hexane is isomerised to form
2-methyl pentane, then octane number increases from 25 to 74.
 Reaction Chemistry of Reforming
3) Dehydrocyclisation of paraffin's This reaction is a difficult reaction as it
involves both cyclisation and dehydrogenation of paraffin. It is
favoured by low pressure and high temperature. One example of this
type of reaction is the conversion of n-heptane having zero octane
number in the octane scale to methylcyclohexane, having octane
number 75.
4) Hydrocarcking of paraffin's Hydrocracking of paraffin's is a reaction
which occurs with the hydrogen liberated from other reactions of
reforming. It is a high temperature and high pressure process. In this
process some unwanted lighter products are obtained which boil
below gasoline range. Hence, total liquid yield is diminished.
 Types of reforming process
Semi-Regenerative Reforming (SRR) is the most common type of the catalytic
reforming unit. This process is continuously carried out for a long period of time
and catalyst activity gets reduced with time due to coke deposition. As the activity
of the catalyst decreases, the aromatics conversion and the yield of hydrogen
decreases. Hence to maintain almost constant yield, the reactor temperature is
increased as catalyst activity declines. When the catalyst activity decreases to a
very low level, which is called ‘end-of-cycle’, catalyst regeneration is started in situ
by shutting down the reactor. Usually, SRR is operated at high pressure to
maximize the time gap between two successive regenerations. High reactor
pressure minimizes coke formation on the catalyst. The time gap between two
successive regeneration is usually 6–24 months. The Pt–Re catalyst is suitable
catalyst for SRR units because it can tolerate high coke deposition and regenerates
easily. The semi-regenerative system is generally designed keeping three to four
catalyst reactors in series.
 Types of reforming process
Continuous Catalytic Regenaration (CCR) is the recently developed and most modern type of
the catalytic reformers. A schematic of the process is shown in Fig 1. In this process the
regeneration of catalyst is done continuously in a special regenerator and then the
regenerated catalysts are charged to the operating reactors. CCR process can handle low
quality naphtha feed and produce high octane number. Hydrogen yield is also high in this
process. Platinum/tin on alumina catalyst is mainly used in CCR process as the addition of
tin enhances the selectivity to aromatics, improves stability, and regeneration ability of
Pt/Al2O3. Reactors may be arranged either separately one after the other or stacked on top
of one another and the catalyst moves from the bottom of one reactor to the top of the
next reactor. The regenerated catalyst is charged to the first reactor and the deactivated
catalyst is withdrawn from the last reactor and sent back to the regenerator. The difference
between SRR and CCR process is that, selectivity towards aromatics is more important in
CCR process than SRR, while tolerance of high coke deposition of the catalyst is one of the
prime factor in SRR as the regeneration cycle time is much more here, than that of CCR.
 Process description
Naphtha feed after hydrotreatment to lower the sulphur and nitrogen
content, is mixed with the hydrogen formed in the process and
introduced into a heater. Then the hot feed is charged to the first
reactor at around 5000F temperature and 500 psig pressure. In this
reactor, the fast endothermic naphthene dehydrogenation reaction
takes place. Due to endothermic reaction the temperature of the
feed falls down. The feed is then sent to the second reactor through
a second heater. After other reactions take place at this stage, the
feed is finally sent to the third reactor via third heater where final
reactions occur. The hydrogen produced in the process is collected
and recycled in the process.
 Process description
Reformate produced is heat exchanged and sent to a fractionator
to remove light products to stabilize it. The high octane
reformate is collected at the bottom of the fractionator at
specified Reid vapour pressure. Catalyst deactivation is
minimized by maintaining high hydrogen to hydrocarbon molar
ratio (~6:1).
The CCR process has the advantage of regenerating the catalyst
continuously hence the catalysts are essentially contributing its
original activity all the time in the reactor. So, the unit can
operate at lower pressure upto 50 psig regardless of coke
deposition on the catalyst.
END