CATALYTIC REFORMING

Introduction
With the fast growing demand in aromatics and

demand of high - octane numbers, catalytic

reforming one of the most important unit
processes in the petroleum and petrochemical
industry.
The reforming process is a catalytic process
which converts low octane naphtha into higher
octane reformate products for gasoline blending
and aromatic rich reformate for aromatic
production.
Naphtha feeds to catalytic reforming include
heavy straight run naphtha.
It transforms low octane naphtha into highoctane motor gasoline blending stock and
aromatics rich in benzene, toluene, and xylene

Various Types of Catalytic Reformers

Semi-Regenerative Fixed Bed reactors: In

this type of reformers the catalyst has a life of

one or more years between regeneration. The
time between two regeneration is called a cycle.
The catalyst retains its usefulness over multiple
regeneration.
Cyclic Fixed Bed Reformers: Cyclic reformers
run under more severe operating conditions for
improved octane number and yields. Individual
reactors are taken by a special valving and
manifold system and regenerated while the
other reformer unit continues to operate.
Continuous Reformers: In these reformers
the catalyst is in moving bed and regenerated
frequently. This allows operation at much lower

Reactions in catalytic reforming

The major reactions in catalytic reforming are:
Dehydrogenation of naphthenes to aromatics
Isomerization of paraffins and naphthenes
Dehydrocyclization of paraffins to aromatics
Hydrocarcking of paraffins to lower molecular
weight of naphthenes.
Some of the other reactions are:
Demethylation
Hydrodealkylation
Catalyst coking

Dehydrogenation :
Highly endothermic, and it causes a decrease
in temperatures as the reaction progresses.
Highest reaction rates, aromatics formed so
end point of gasoline rises.
Favorable Conditions: High temperature,
Low pressure, Low space velocity, Low H2/HC
ratio increases the yield.
Cyclohexane Benzene + H2
Methyl cyclohexane Toluene + H2

ISOMERIZATION:
Two types of reactions are involved:
Isomerization of normal paraffins to Isoparaffins AND Iso-paraffins to aromatics
Isomerization of cyclopentanes to cyclohexanes
plus subsequent conversion into benzene.
High temperature, low space velocity, and low
pressure increase Isomerization yield.
Reaction is exothermic
Methyl cyclopentanes Cyclohexane
Benzene + H2

Dehydrocyclization:
The most critical reactions in reforming are

much slower and are favored by high

temperature and low pressure.
A minimum six carbon chain needed to cyclize
to form aromatics.
The conversion of paraffins to naphthenes
increases with an increase in paraffin carbon
number.
This reaction is promoted by catalytic
functions.
Favorable Conditions: High temperature,
Low pressure, Low space velocity, Low H2/HC
ratio increases the yield

Hydrocracking:
Hydrocracking is the breaking of C-C bond in the forming

process giving to irreversible formation of lower molecular

weight paraffins with less valuable products.
Conversion of normal, iso, and cyclo paraffins to lower
molecular weight paraffins increases with an increase in
temperature and pressure and the conversion increases as
space velocity decreases.
Cracking of cyclo paraffins also increases with temperature
and residence time in the reactors.
These are endothermic.
C7H16 + H2 C3H8 + C4 H10
n-heptane
n-propane
n-butane
C10H22 + H2 C6H14 + C4H10
n-decane
n-hexane
n-butane
C10H22 + H2 C7H16 + C3H8
n-decane
n-heptane npropane

Hydrodealkylation:
It is favored at high temperature, low
pressure and low space velocity.
The reactions are endothermic.
Toluene + H2 Benzene + CH4

Hydrocracking is controlled by operating

the reaction at low pressure between 525
atm, not too low for coke deposition and
not too high in order to avoid cracking and
loss of reformate yield.

Coke formation:
It is a natural byproduct and results from

intensive cracking of hydrocarbons and is favored

by high temperature and low pressure and this
affects the activity of the catalyst.
The activity of the catalyst and its selectivity for

the desired product decreases over a period of

time due to formation of coke on the surface of
catalyst.
The rate of coke deposition is dependent on

operating conditions, feed composition and

nature of the catalyst.

Favorable Conditions for Different

Reforming Reactions
Reaction

Pressure

Temperatur
e

Dehydrogenation of
naphthenes to
aromatics

Low pressure

High temperature

Isomerization of
naphthenes

Indeterminate

Indeterminate

Dehydrocylization
of
paraffins to
aromatics

Low pressure

High temperature

Hydrocracking

High pressure

High temperature

Reforming catalyst
The first catalyst used in catalytic reforming was

molybdenum oxide on alumina to catalyze

hydrogenation and dehydrogenation reactions to
produce high octane gasoline.
Reforming catalyst activity is a function of surface area,

pore volume and active platinum and chlorine content.

Reforming catalyst contain platinum with or without
promoting metals dispersed uniformly on high purity
chlorinated alumina support containing chlorine, rhenium,
iridium, tin or germanium.
Some of the advantages of the bimetallic catalysts are:

Enhanced resistance to coking,

Lower pressure and low H/HC operation resulting high octane number
High aromatics and high yield of desired product
Better yield stability
Lower temperature requirement
Better tolerance to high temperature
High ultimate life

Reforming Processes
The various reforming processes can be characterized
in four major categories depending upon the
frequency of catalyst regeneration.
Semi Regenerative (SR);
Continuous Catalyst Regenerative (CCR)
Cyclic and
Hybrid ;
Catalytic reforming SR, CCR, Cyclic and Hybrid
Magnaforming SR and Semi cyclic
Platforming SR, CCR
Power forming- Cyclic and SR

SR is the most commonly used technology

from moderate to serve type of operations

and uses series of fixed bed reactors.
CCR uses moved bed technology and operates
at much lower pressure compared to SR.
The Cyclic process is a compromise between
the SR & CCR and is characterized by an
additional swing reactor, which is brought on
stream when any one of the reactors is to be
regenerated.
Hybrid process is a combination of SR and
CCR or Cyclic type.

operating conditions of three

reforming processes

The catalytic reforming process involves

treatment of naphtha feedstock for

removal of impurities such as sulphur,
nitrogen, and metals which poison the
reformer catalyst.
The treated naphtha mixed with
hydrogen is preheated and charged to
series of four reactors with interposed reheaters.
Operating conditions: temperature- 4505250C; Pressure 7-30 bar; H/HC 5-8;
As the reaction in reforming
endothermic, the product from each

The reactors are may be radial or axial flow type.

It should provide good flow distribution and lower

pressure drop
The reactor effluent from the last reactor at a
temperature of 5000C goes to product recovery
section which separation of hydrogen and light
hydrocarbons takes place in the flash separator from
where the hydrogen rich gases are recycled.
The liquid stream from separator goes to the
fractionator from where the bottom reformate to sent
to storage tank for further processing.
Catalyst activity reduced due to formation of coke,
olefins, diolefins and sulphur, nitrogen water and
halogens.

Process variables in Catalytic Reforming

Following variables affect the reformate yield

and quality of the product in the reforming
process:
Reaction temperature, Space velocity,
Reaction pressure, H2/HC ratio, Feedstock
Characteristics, Catalyst type and Catalyst
poisons.
Aromatic yield can be increased by raising
the temperature, lowering the pressure and
lowering the H2/HC ratio.

Feed Quality:
The feedstock properties greatly affect the reformate

yield and aromatic content of reformate.

Naphthenes dehydrogenate very fast and thus high
naphthenic feed gives the highest reformate yield
whereas feedstock having paraffins require more
severe conditions and give lower reformate yields.
N + 2A are commonly used to judge the reformer yield.
With higher N + 2A , aromatic yield will be high.
Characterization factor = 12.6 (N+2A)/100
Light fractions have poor naphthene and aromatic
content and poor feed for reforming. It results lower
aromatic and H2 yield.
Heavy fractions which contain higher naphthene and
aromatic content are preferred feedstock for reforming.

Temperature:
It is most important operating parameter in the reforming process

and a simple change in the reactor inlet temperature can affect the
octane number and product quality.
Normally reforming reactor inlet temperature is maintained at 4705500C.
An increase in temperature will result in increase in octane
number, decrease in the yield C5+ fraction, decrease in H2 purity,
increase in coke deposit.

Space velocity:
The space velocity in the reforming process is linked with the

contact time in the reformer.

Lower space velocity the severity will be higher keeping the all
other conditions same.
Lower space velocity results in increase in octane number,
decrease in the product yield, decrease in the H2 purity, and
increase in the coke deposit.
Higher naphthenic feedstock requires high space velocity whereas
more paraffinic stocks requires lower space velocities.
Reforming space velocity range is 1.0-3.0 hr -1

REACTION PRESSURE
Reforming reaction pressure ranges (5 35 kg/sq. cm.). Decreasing
pressure increases dehydrogenation of naphthenes and
dehydrocyclization of paraffins which favors an increase in
production of aromatics and hydrogen (increase catalyst coking
and shorter cycle life).
Higher pressure causes higher rates of hydrocracking reducing
reformate yield but decreases coking of catalyst resulting in longer
cycle life.
Hydrogen: Hydrocarbon Ratio
Hydrogen: Hydrocarbon Ratio = Moles of H2 in Re cycle

Gas/ Moles of Hydrocarbons.

Higher the H2/HC ratio, higher the cyclic length. Two main
reasons for reducing H2:HC ratio :
Reduction in energy costs for compressing and circulating H2.
Favors naphthene dehydrogenations and dehydrocyclisation

reaction
Lowering of H2/HC Ratio, From 8 to 4 carbon increase in

1.75 times and from 4 to 2 carbon increase 3.6 times

Catalyst Poisoning:
Temporary Poisons: Temporary poisons are
those impurities which can be removed during
various pretreatment process like sulphur,
nitrogen,
Permanent Poisons: Permanent Poisons are
those impurities present in the feed which is
irreversible damage to the catalyst
Source and maximum level of catalyst poisons
are given in Table.