10

Catalytic Reforming and

Isomerization
Introduction
• The demand of today’s automobiles for unleaded high-octane
gasolines has stimulated the use of catalytic reforming.
• In catalytic reforming, the change in the boiling point of the stock
passed through the unit is relatively small.
• Catalytic reforming primarily increases the octane of motor gasoline
rather than increasing its yield.
• In fact, there is a decrease in yield because of hydrocracking reactions
that take place in the reforming operation.
Feedstock
• The typical feedstocks to catalytic
reformers are heavy straight-run (HSR)
naphthas [180 to 375°F (82 to 190°C)]
and heavy hydrocracker naphthas.
• These are composed of the four major
hydrocarbon groups: paraffins, olefins,
naphthenes, and aromatics (PONA).
• Typical feedstock and reformer Why no LSR Naphtha in feed?
products have the following PONA The ease and probability of
analyses (vol %): reforming increases with the number
of carbon atoms in the molecules.
10.1 REACTIONS

Desirable reactions Undesirable reactions

1. Paraffins are isomerized and to some 1. Dealkylation of side chains
extent converted to naphthenes. The
naphthenes are subsequently on naphthenes and
converted to aromatics. aromatics to form butane
2. Olefins are saturated to form and lighter paraffins
paraffins, which then react as in (1).
2. Cracking of paraffins and
3. Naphthenes are converted to
aromatics. naphthenes to form butane
4. Aromatics are left essentially and lighter paraffins
unchanged.
• There are four major reactions that take place during reforming. They
are
1. dehydrogenation of naphthenes to aromatics,
2. dehydrocyclization of paraffins to aromatics,
3. isomerization, and
4. hydrocracking.
10.1.1 DEHYDROGENATION
REACTIONS
• The dehydrogenation reactions are highly endothermic and cause a
decrease in temperature as the reaction progresses;
• dehydrogenation reactions have the highest reaction rates of the
reforming reactions,
• which necessitates the use of the inter-heaters between catalyst beds
to keep the mixture at sufficiently high temperatures for the reactions
to proceed at practical rates.
• Aromatics have a higher liquid density than paraffins or
naphthenessame number of carbon atoms
• 1 volume of paraffins produces only 0.77 volume of aromatics, and 1
volume of naphthenes about 0.87 volume.
• In addition, conversion to aromatics increases the gasoline end point,
because the boiling points of aromatics are higher than the boiling
points of paraffins and naphthenes with the corresponding number of
carbons.
• The yield of aromatics is increased by:
• High temperature
• Low pressure
• Low space velocity
• Low hydrogen-to-hydrocarbon mole ratios
10.1.2 ISOMERIZATION REACTIONS
• Isomerization of paraffins and cyclopentanes usually results in a lower
octane product than does conversion to aromatics. However, there is
a substantial increase over that of the un-isomerized materials.
• Isomerization yield is increased by
1. High temperature (which increases reaction rate)
2. Low space velocity (which increases reaction time)
3. Low pressure
• There is no isomerization effect due to the hydrogen-to-hydrocarbon
mole ratios, but high hydrogen-to-hydrocarbon ratios reduce the
hydrocarbon partial pressure and thus favour the formation of
isomers.
10.1.3 HYDROCRACKING REACTIONS
• The hydrocracking reactions are exothermic and result in the
production of lighter liquid and gas products. They are relatively slow
reactions, and therefore most of the hydrocracking occurs in the last
section of the reactor. The major hydrocracking reactions involve the
cracking and saturation of paraffins.
• The concentration of paraffins in the charge stock determines the
extent of the hydrocracking reaction.
• Hydrocracking yields are increased by
• High temperature
• High pressure
• Low space velocity
10.2 FEED PREPARATION
• The active material in most catalytic reforming catalysts is platinum.
• Certain metals, hydrogen sulfide, ammonia, and organic nitrogen and sulfur
compounds will deactivate the catalyst.
• Feed pretreating, in the form of hydrotreating, is usually employed to remove
these materials.
• The hydrotreater employs a cobalt-molybdenum catalyst to convert organic
sulfur and nitrogen compounds to hydrogen sulfide and ammonia, which then
are removed from the system with the unreacted hydrogen.
• Any metals in the feed are retained by the hydrotreater catalyst.
• Hydrogen needed for the hydrotreater is obtained from the catalytic reformer.
10.3 CATALYTIC REFORMING
PROCESSES
major reforming processes Basic reforming processes
• Platforming • Basic reforming processes are
• Powerforming classified as (depending upon
the frequency of catalyst
• Magnaforming regeneration):
• Reforming • Continuous
• Ultraforming • Cyclic
• Semi-regenerative
• Catalytic Reforming
Process Description (Semi-regenerative
Process):
• The preheated feed and the recycle hydrogen are heated to 925 to
975 degree F (498 to 524 degree C) before entering the first reactor.
• In the first reactor, the major reaction is the dehydrogenation of
naphthenes to aromatics, and as this is strongly endothermic, a large
drop in temperature occurs.
• To maintain the reaction rate the gases are reheated before being
passed over the catalyst in the second reactor.
• As the charge proceeds through the reactors, the reaction rates
decreases and the reactors becomes larger, and the reheat needed
becomes less.
• Usually three or four reactors are sufficient to provide desired degree
of reaction, and heaters are needed before each reactor to bring the
mixture up to reaction temperature.
• In practice, either separate heaters can be used or one heater can
contain several separate coils.
• A typical gas composition leaving each of the reactors in a four-
reactor system, with an HSR naphtha feed of 180 to 380°F; severity,
99 RON; and pressure, 163 psi (1124 kPa), is as follows [4]:
• The reaction mixture from the last reactor is cooled, and the liquid
products condensed.
• The hydrogen-rich gases are separated from the liquid phase in a
drum separator and the liquid from the separator is sent to a
fractionator to be debutanized.
• The hydrogen-rich gas stream is split into a hydrogen recycle stream
and a net hydrogen by-product, which is used in hydrotreating or
hydrocracking operations or as a fuel.
Process Description (Continuous Process):
• The continuous catalyst regeneration unit moves the catalyst between
the reactor and regenerator and permits the catalyst to be
regenerated and returned to the reactor while the unit is operating.
• The catalyst flows by gravity through the reactor.
• It is then picked up in a nitrogen stream and carried to the top of the
regeneration unit.
• As the catalyst flows through the regenerator, the coke is burned from
the catalyst using a nitrogen stream containing a small amount of
oxygen.
• The oxygen content is carefully regulated to prevent the catalyst from
overheating and becoming permanently deactivated.
• After regeneration, it is carried in a hydrogen stream to the top of the
reactor to begin its journey through the cycle again.
• From the time a catalyst particle enters the top of the reactor until it
goes through the cycle and is returned to the top of the reactor a
period of 5 to 7 days is required.
Process Description (Cyclic Process):
• The cyclic process is a compromise between these extremes and is
characterized by having a swing reactor, in addition to those on-stream,
in which the catalyst can be regenerated without shutting the unit
down.
• When the activity of the catalyst in one of the on-stream reactors drops
below the desired level, this reactor is isolated from the system and
replaced by the swing reactor containing freshly regenerated catalyst.
• The catalyst in the replaced reactor is then regenerated by admitting hot
gas containing about 0.5% oxygen into the reactor to burn the carbon
off the catalyst.
Catalyst Generation:
• The original reforming process is classified as a semiregenerative type
because catalyst regeneration is infrequent and runs of 6 to 24
months between regenerations are common.
• In cyclic processes, regeneration is typically performed on a 24-48
hour cycle, and a spare reactor is provided so that regeneration can
be accomplished while the unit is still on-stream.
• Because of these extra facilities, the cyclic processes are more
expensive but offer the advantages of lower pressure operation and
higher yields of reformate at the same severity.
Self-Study
• Type of catalysts used?
• Which catalyst is being used for what purpose?
• Reforming catalyst activity is a function of what?
• Why catalyst activity is reduced?
• How much amount should be processed before catalyst need/require
regeneration?
• How catalyst activity can be restored?
• Why operation severity is reduced?
• What is meant by the term “In-situ catalyst regeneration”?
Reactor Design
• Fixed bed reactors used for semiregeneration and cyclic catalytic
reforming are very similar to those used for hydrotreating,
isomerization, and hydrocracking.
• These reactors have an internal refractory lining that is provided to
insulate the shell from the high reaction temperatures and thus
reduce the required metal thickness.
• Metal parts exposed to the high-temperature hydrogen atmosphere
are constructed from steel containing at least 5% chromium and 0.5%
molybdenum to resist hydrogen embrittlement.
• Proper distribution of inlet vapor is necessary to make maximum use
of the available catalyst volume.
• Some reactor designs provide for radial vapor flow rather than the
simpler straight-through type shown here.
• The important feature of vapor distribution is to provide maximum
contact time with minimum pressure drop.
• Temperature measurement at a minimum of three elevations in the
catalyst bed is considered essential to determine catalyst activity and
as an aid in coke burn-off operations.
• The catalyst pellets are generally supported on a bed of ceramic
spheres about 12 to 16 in. (30 to 40 cm) deep. The spheres vary in
size from about 1 in. (25 mm) on the bottom to about 0.35 in. (9 mm)
on the top.
10.7 ISOMERIZATION
• Isomerization alters the arrangement of atoms without adding or
removing anything from the original material.
• Isomerization is used to convert normal butane into isobutene, an
alkylation process feedstock, and normal pentane and normal hexane
into isopentane and isohexane, high-octane gasoline components.
• The light naphtha stream from the crude tower, coker, and cracking
units is sent to an isomerization unit to convert straight-chain
paraffins into isomers that have higher octane number.
• The octane numbers of the LSR naphtha (C5- 180 degree F (C5- 82 degree C))
can be improved by use of an isomerization process to convert normal
paraffins to isomers.
• This results in significant octane increases.
• N-pentane has an unleaded (clear) RON of 61.7 and isopentane has a rating of
92.3.
• Reaction temperatures of about 200 to 400 degree F (95 to 205 degree C) are
preferred to higher temperatures because the equilibrium conversion to
isomers is enhanced at the lower temperatures.
• At this low temperature, a very active catalyst is necessary to provide a
reasonable reaction rate.
Once-through vs Recycle process:
• In once-through isomerization where the normal and iso compounds
come essentially to thermodynamic equilibrium, the unleaded RON of
LSR naphtha can be increased from 70 to about 82 to 84.
• If normal components are recycled, the resulting research octane
numbers will be about 87 to 93 RON.
Type of Catalysts Used:
• The available catalysts used for isomerization contain platinum on
various bases.
• Some type of catalysts (alumina support) require the continuous
addition of very small amounts of organic chlorides to maintain high
catalyst activities.
• This is converted to hydrogen chloride in the reactor, and
consequently the feed to these units must be free of water and other
oxygen sources in order to avoid catalyst deactivation and potential
corrosion problems.
• A second type of catalyst used a molecular sieve base and is reported
to tolerate feeds saturated with water at ambient temperatures.
• A third type of catalyst contains platinum supported on a novel metal
oxide base.
• This catalyst has a 83 degree C higher operating temperature than
conventional zeolitic isomerization catalysts and can be regenerated.
• Catalyst life is usually 3 years or more with all of these catalysts.
Important Points:
• An atmosphere of hydrogen is used to minimize carbon deposits on
the catalyst.
• The actual product distribution is dependent upon the type and age
of the catalyst, the space velocity, and the reactor temperature.
• The pentane fraction of the reactor product is about 75 to 80 wt. %
isopentane, and the hexane fraction is about 86 to 90 wt. % hexane
isomers.
• Following table is a simplified conversion summary for a typical LSR
cut.

• Separation of the normal from the isomers can be accomplished by

fractionation or by vapor phase adsorption of the normal on a
molecular sieve bed.