CATALYTIC REFORMING

Catalytic reforming is a major conversion

process
in
petroleum
refinery
and
petrochemical industries.
The reforming process is a catalytic process
which converts low octane naphthas into
higher octane reformate products for gasoline
blending and aromatic rich reformate for
aromatic production.
Basically, the process re-arranges or restructures the hydrocarbon molecules in the
naphtha feedstocks as well as breaking some
of the molecules into smaller molecules.

 Reformer feed is either:

-Low quality straight run naphtha
-cracked naphtha, generally mixed with straight run
naphtha.
-It transforms low octane naphtha into high-octane motor
gasoline blending stock and aromatics rich in benzene,
toluene, and xylene with hydrogen and liquefied
petroleum gas as a byproduct.

Reformer feed pretreatment

Due to the presence of contaminants in all cases and to the
specific characteristics of cracked naphtha, Naphtha
Pretreating unit(s) is(are) always necessary

Chemical reactions
Two types of reactions
involved in the process:
Desirable reactions, which
lead to a higher octane
number and to high purity
hydrogen production. They
are the reactions to
promote
Adverse reactions, which
lead to a decrease of
octane number and a
decrease in hydrogen
purity. They are the
reactions to minimize

RON

MON

Cyclohexane

83

77.2

Methylcyclohexane

74.8

71.1

1.3 dimethylcyclohexane

71.7

71.

Benzene

114.8

> 100

Toluene

120

103.5

m-Xylene

117.5

115.

RON:
MON:

Research Octane Number

Motor Octane Number

Desirable reactions with hydrogen

production

Naphthenes
dehydrogenation
Naphthenic compounds dehydrogenated into aromatics with
production of 3 moles of H2 per mole of naphthene
Highly endothermic

Thermodynamically favored by high temperature, low pressure

CH

CH

HC
2

CH

HC

CH

+ 3H
HC
2

CH
CH

Cyclohe xane

HC

CH
CH

Benzene

Desirable reactions with hydrogen

production

Paraffin's dehydrocyclization
Multiple step reaction

CH

Kinetically favored by high

temperature, and low
pressure

CH

CH

CH
2

CH

CH

2
CH
3

CH
2

CH
3

CH

+H
CH CH 2
3

CH
7 14

CH
3

CH
2

CH
2

CH
2

CH
2

CH 2

CH

CH

CH

CH
7 16

CH

CH
2

CH
CH

HC
2
CH
2

CH

Methylcyclohexane
CH
2

CH

CH

CH
C

CH

HC
2
CH

CH

CH

CH
3

HC
CH

CH

+ 3H
2

Desirable reactions with hydrogen

production

Linear paraffin's isomerization

Slightly exothermic
Fast
favored by high temperature

CH
7 16

CH
7 16

Desirable reactions with hydrogen

production

Naphthenes isomerization

Desirable reaction because of the subsequent dehydrogenation of the

alkylcyclohexane into an aromatic
Slightly endothermic

RON

MON

Ethylcyclopentane

= 67.2

61.2

Methylcyclohexane

= 74.8

71.1

Toluene

= 120

103.5

Adverse reactions
Hydrocraking
Hydrocracking affects

(m)
+H
2
CH
7 16

either paraffins or
olefins
Favored by high
temperature and high
pressure
Exothermic

CH
7 14
(a)
+

+H
CH
7 14

2
CH
4 8

(m)
+H
CH
4 8

CH
4 10

C 3H

Adverse reactions
Hydrodealkylation

Breakage of the branched radical of an aromatic ring

Favored by high temperature and high pressure
Consumes hydrogen and produces methane
But at the selected operating conditions, and with the selected
catalyst, this reaction is not significant

+H

+ CH

Xylene

Toluene

+H

+ CH
2

Toluene

Benzene

Adverse reactions
Alkylation
Addition of an olefin molecule on an aromatic ring

leads to heavier molecules

High tendency to form coke; must be avoided

CH3
+ CH2= CH CH3
Benzen
e

Propylen
e

HC
Isopropylbenzen
e

CH
3

Adverse reactions
Coking
Results from a complex group of reactions.
Linked to heavy unsaturated products (polynuclear aromatics)
and heavy olefins traces or diolefins present in the feed or in
CCR reactions
Coke deposit reduces active contact area and reduces
catalyst activity
Favored by low pressure

Catalyst
The main characteristics of a catalyst other than its physical
and mechanical properties are :
The activity
o catalyst ability to increase the rate of desired
reactions
o Is measured in terms of temperature
The selectivity
o Catalyst ability to favor desirable reactions
o Practically measured by the C5+ Reformate and
Hydrogen yields
The stability
o Change of catalyst performance ( activity, selectivity )
with time
o Caused chiefly by coke deposit and by traces of metals
in feed
o Measured by the amount of feed treated per unit
weight of catalyst. C5+ wt reformate yield is also an
indirect measure of the stability.

Catalyst
Reforming catalysts are bimetallic catalyst consisting of platinum
plus promoters on an alumina support, . The second metal comes
from the group(promoter besides the others metal)
^Rhenium (Re)
^Tin (Sn)
^Iridium (Ir)
^Germanium (Ge)
The main features of these catalysts are :
o High purity alumina support - High mechanical
resistance
o Platinum associated with Rhenium - high stability &
selectivity
o Platinum associated with Tin high selectivity
o High Regenerability
The combination of these qualities
advantages:
o High Reformate yield
o High hydrogen yield
o Low catalyst inventory

give

the

following

Process Variables

Pressure

Low pressures enhance hydrogen producing

dehydrogenation, dehydrocyclisation, coking
Cracking rate is reduced

Temperature

increase of temperature has the following

effects:
Increases octane
Decreases the yield (of C5+ fraction)
Increases the coke deposit

Space velocity

Quality of the feed

Conventional Unit
Axens, UOP
Chevron, Amoco, Exxon, Engelhard)

Booster
Compressor

HydrogenRich Gas

Separator

Recontacting
Drum

Unstabilized
Reformate

Feed
Recycle
Compressor

16
Catalytic Reforming

Dualforming
Reactors
R
e

C
R
R
X

Booster
Compressor

Hydrogen
Rich
Gas

g
e
n
C

Recontacting
Drum

Feed
Recycle
Compressor

Unstabilized
Reformate

Continuous Catalytic
Regenerative
Reforming

Objectives of Regeneration Section

Recover initial catalyst activity

Coke removal

Metal redistribution &

chloride adjustment

Catalyst drying