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
