Reforming

Reforming means a rearrangement of molecules without much affecting the

average weight of feed which is generally naphtha of gasoline boiling point
range.
Reforming is carried out to produce high-quality (Octane number) gasoline
by heating the naphtha with or without a catalyst.
Low octane number thermally cracked gasoline (is also a feed for
reforming) is also subjected to reforming to improve its quality(octane
number).
Feed for reforming:
The feed is generally naphtha produced during the straight run distillation of
crude oil, catalytic cracking, and coking process.
Reforming Products:
Besides the main product i.e. reformate or reformed gasoline, reforming also
produces lighter hydrocarbons (gases), hydrogen, and traces of very high boiling
materials.
The hydrogen-rich gaseous product is recycled with naphtha feed.

The desirable reactions during reforming tend to produce high octane number
hydrocarbons from lower ones.

Aromatics have the highest octane number. Octane number increases in the
order Paraffin olefin naphthalene iso-paraffin
aromatic
 Various Reforming Reactions
Dehydrogenation of naphthene to aromatic

Dehydroisomerization

Hydroisomerization - conversion of one isomeric form into another of alkane hydrocarbons via
an
alkene intermediate
Various Reforming Reactions
Dehydrocyclization of paraffin to aromatic

Isomerization

N paraffins are converted into iso paraffins which Have higher octane
number.
Various Reforming Reactions
Hydrocracking of higher paraffin to lower paraffin

Dehydrogenation of n-paraffins to olefins

Though olefins have higher octane number than corresponding n

paraffins, still this reaction is undesirable because lower olefins
polymerize to produce gummy materials which is
Thermal Reforming:
This is carried out in the absence of a catalyst and is similar to high-temperature,
low-pressure thermal cracking.
Feed is usually naphtha and the products are mainly gas(13-14%) and gasoline (75-
80%) of octane number 81-86, rest being polymer (unwanted gum) and losses.
Catalytic Reforming:

Two types of Catalyst

 Nonprecious metal oxide type (molybdena or chromia supported on alumina base)

 Precious metal oxide type (platinum on a silica-alumina or alumina base)

Platinum is a more active and selective catalyst, however, it is easily poisoned by

compounds containing Sulphur, nitrogen, arsenic etc., and needs pretreatment of the
feed for the removal of these impurities.

A catalyst may be in the form of powder, bead, or pellet.

Various commercial catalytic reforming processes are platforming,

Catforming, Hydroforming, Fluidized Hydroforming and

Thermofer Catalytic Reforming (TCR).

The reactor conditions are normally in the range of T =450 -550oC and

P = 15-45 kg/cm2
Effect of variables in catalytic Reforming:

Effect of temperature:
The temperature is in the range of 450 -550oC.
If the temperature is less than 450oC, the catalyst is inactive whereas if
temperature exceeds 550oC then hydrocracking predominates.
Cyclisation occurs at 470-490oC whereas isomerization at 40-50oC.
Dehydrogenation reaction occurs upto 500-550oC. At 700-800oC, olefin
formation starts.
Effect of pressure:
Dehydrogenation of naphthene is desirable, which is favoured by low
pressure and high temperature, however this condition also favours the
formation of coke which deactivates the catalyst.
Deposition of coke can be reduced by operating in an atmosphere of
hydrogen; higher the pressure of hydrogen, the slower is the coke
deposition. Increasing the pressure of hydrogen does not severely
retards the dehydrogenation of naphthenes which produce high octane
number aromatics.
Hence, catalytic reforming is carried out under substantial pressure with
the hydrogen product recycled to the reaction zone.
As pressure and hydrogen recycle ratio is increased, gasoline yield
reduces.
Effect of catalyst particle size:
With very active catalyst, the interior portion is ineffective because reaction
occurs before the reactants can penetrate to the core. In this situation, the
activity of the catalyst increases as the particle size is reduced.

Effect of trace materials in feed:

High Sulphur in feed inhibits dehydrogenation and promotes
hydrocracking over platinum catalyst thereby reducing the yield of
liquid products.

High Sulphur concentration also accelerates deactivation of catalyst.

Presence of nitrogen in feed, inhibits dehydrocyclization of paraffin and

hydrocracking.
Metals such as lead and arsenic poison the catalyst.
Commercial catalytic reforming processes

Fluidized bed – Fluidized hydroforming process

Non-Regenerative Fixed Bed Platforming process
One of the most widely used process.

Catalyst: platinum and halogen on

alumina base.

200 barrels of feed per pound of

catalyst.

Reactor temperature 455-530oC

Pressure 33-47 kg/cm2

Reactor space velocity 1.5 to 3

volume
of feed per hour per volume
of catalyst
Regenerative Fixed Bed Hydroforming Process
This process uses a catalyst containing 8-10% of molybdena on an
alumina support.
Temperatures of 480-540°C and pressures from 14 to 20 kg/cm2 are
used.
The catalyst beads are regenerated after 4 to 8 hours operation. Both
upflow and downflow regeneration is done to hold the temperature
between 565 to 595°C.
A high partial pressure of hydrogen is maintained during hydroforming
process by recycling the hydrogen produced by the dehydrogenation of
naphthene and cyclisation of parafins.
Desulphurisation also takes place, most of the sulphur present being
removed as hydrogen sulphide. Gasoline yield is more than 75% with an
octane number of 80-85 (unleaded).
Thermofer Catalytic Reforming (TCR) Moving Bed
Process
Thermofer Catalytic Reforming (TCR) Moving Bed Process
TCR process uses a single reactor operating at 12 kg/cm2 and 510-540°C.
A catalyst regenerating kiln operating at atmospheric pressure and 540-570°C is used to
remove coke from the deactivated catalyst.
Catalyst is used in the form of beads and contains about 32% chromia on alumina base.
Since, it is fairly resistant to poisons in feedstock, no pretreating of feed is necessary.
After being heated separately, the feedstock and recycle stream are combined and enter
the reactor. Reactor space velocity is maintained at 0.7 volume oil per hour per volume
catalyst. The catalyst to oil ratio (volume) is 0.3.
The products are cooled and then sent to fractionator where recycle gas stream and liquid
reformate are separated. Catalyst is injected from top hopper and after moving down the
reactor goes to a depressurising leg and then to the regenerator.
About 25 tons/hr of catalyst circulates in a reformer designed for 15000 barrels of
naphtha/day. Normal catalyst attrition rate is about 0.2 lb/barrel of feed.
Fluidized Bed Hydroforming Process
Fluidised Bed Hydroforming Process
In this process, a powdered catalyst containing 10% of molybdena and 90%
alumina circulated between a reactor and a regenerator by the fluidised
technique. Fluid hydroformers operate at 480°C and 14-20 kg/cm2 (same as fixed
bed hydroforming unit).
To maintain this reaction temperature while supplying the endothermic heat of
the reaction, the recycle gas is heated to 650°C. The feed temperature is kept
below 540°C to minimise thermal cracking.
Fluidisation enables the temperature to be controlled in the reactor very closely
preventing the excessive reforming with production of gases that take place in
fixed bed units. Similarly, regeneration temperature is more closely controlled by
the use of cooling coils in the regeneration unit.
Catalyst circulation rate is about 1 kg catalyst per kg naphtha charge. A gasoline
yield of about 80% with octane number of 95 (unleaded) can be obtained by this
process.