1

Catalytic Reforming
CATALYTIC REFORMING
Process,Catalysts and Reactors
CATALYTIC REFORMING
Process,Catalysts and Reactors
Mohan Lal
Axens India Private Limited
(PrivateLimited Company formed under the
Companies Act, 1956)
on
Petroleum Federation of India
Indian Oil Corporation Ltd. (Haldia Refinery),
&
Lovraj Kumar Memorial Trust
2
Catalytic Reforming
World context:
High octane gasoline requirement
Introduction
3
Catalytic Reforming
World context:
Low sulfur content,
Low benzene content,
Limited aromatics content,
Limited olefins content,
No lead
Introduction
4
Catalytic Reforming
European Gasoline specifications trends
2000 2005 Soon*
Ultimate
Severity**
Sulfur, ppm max 150 50 10 5
Aromatics, vol% max 42 35 30 25
Olefins, vol% max 18 18 14 10
Benzene, vol% max 1 1 1 1
Oxygen, wt% max - 2.7 2.7 2.7
Vapor pressure, kPa
max
90 60 60 50
C5+ ethers, vol%*** 15 15 15 15
Lead, ppb max 5 5 5 5
RON/MON, min 95/85 95/85 95/85 95/85
* Assumed ** Projected final limits 2015 ***banned in several states of USA
Introduction
5
Catalytic Reforming
Gasoline Pool specifications
Bharat
III
Sulfur, ppm max 150
Aromatics, vol% max 42
Olefins, vol% max 21
Benzene, vol% max 1
Oxygen, wt% max -
Vapor pressure, kPa max 60
RON/MON, min 91/81
Introduction
6
Catalytic Reforming
New gasoline specifications require:
Maintaining a high octane level
Meeting reduced sulfur specifications
Meeting reduced Aromatics and Benzene
specifications
Introduction
7
Catalytic Reforming
Constraints from straight run gasoline: Initial fractionation
of crude oils gives gasoline cuts with a low octane number
Light gasoline (C5-C6) : RON between 60 and 70
Heavy gasoline (C7-C10) : RON between 30 and 50
Refiners have to considerably improve the
quality of gasoline cuts to meet RON/MON
specifications
Introduction
8
Catalytic Reforming
RON/MON is increased by chemical transformation
Light gasoline : Isomerization process
n-paraffins i-paraffins
Ex: n-Hexane (RON= 24.8) 2,2-DM Butane (RON=
91.8)
Heavy gasoline: Catalytic Reforming process
n-paraffins, naphtens aromatics
Ex: Cyclohexane (RON = 83) Benzene (RON = 108)
Introduction
9
Catalytic Reforming
Outline
Outline
Fundamentals of Catalytic Reforming
Objective
Reactions desirable and undesirable
Process
Semi Regenerative Reforming
Dualforming
Continuous Catalytic Regenerative Reforming
Process Variables
Reforming Catalyst
Types
Poisons
Some Recent Advances in Reforming
Update on CCR Technology / Catalyst
Update on SR Technology/ Catalyst / Debottle-necking
Options
10
Catalytic Reforming
Fundamentals
Fundamentals
11
Catalytic Reforming
Purpose of reformer
Purpose of reformer
Purpose of reformer

The purpose of Reforming process is to produce : The purpose of Reforming process is to produce :
- - high octane number reformate, which is a main component for m high octane number reformate, which is a main component for motor otor
fuel, aviation gasoline blending or aromatic rich feedstock. fuel, aviation gasoline blending or aromatic rich feedstock.
- - hydrogen rich gas hydrogen rich gas
- - Due to the nature of the reactions, reforming process produces a Due to the nature of the reactions, reforming process produces also: lso:
LPG LPG FG FG 600 psig steam with the waste heat boilers 600 psig steam with the waste heat boilers
12
Catalytic Reforming
Purpose of reformer

Reformer feed
Reformer feed
pretreatment
pretreatment
Due to the presence of contaminants in all cases and to
Due to the presence of contaminants in all cases and to
the specific characteristics of cracked naphtha,
the specific characteristics of cracked naphtha,
Naphtha
Naphtha
Pretreating
Pretreating
unit(s
unit(s
)
)
is(are
is(are
) always necessary.
) always necessary.
Reformer feed is either:
- Low quality straight run naphtha
- or cracked naphtha, generally mixed with
straight run naphtha.
13
Catalytic Reforming
Chemical Reactions
14
Catalytic Reforming
Chemical reactions

Two types of reactions
Two types of reactions
involved in the
involved in the
Octanizing
Octanizing
process:
process:
Desirable reactions Desirable reactions, which , which
lead to a higher octane lead to a higher octane
number and to high purity number and to high purity
hydrogen production. They hydrogen production. They
are the reactions to are the reactions to
promote promote
Adverse reactions Adverse reactions, which , which
lead to a decrease of lead to a decrease of
octane number and a octane number and a
decrease in hydrogen decrease in hydrogen
purity. They are the purity. They are the
reactions to minimize reactions to minimize
RON RON MON MON
Cyclohexane Cyclohexane = = 83 83 77.2 77.2
Methylcyclohexane Methylcyclohexane = = 74.8 74.8 71.1 71.1
1.3 1.3 dimethylcyclohexane dimethylcyclohexane = = 71.7 71.7 71. 71.
Benzene Benzene = = 114.8 114.8 >100 >100
Toluene Toluene = = 120 120 103.5 103.5
m m- -Xylene Xylene = = 117.5 117.5 115. 115.
RON: Research Octane Number
MON: Motor Octane Number
15
Catalytic Reforming

Naphthenes
Naphthenes
dehydrogenation
dehydrogenation
Naphthenic compounds dehydrogenated into aromatics with producti Naphthenic compounds dehydrogenated into aromatics with production on
of 3 moles of H2 per mole of of 3 moles of H2 per mole of naphthene naphthene
Promoted by the metallic function Promoted by the metallic function
Highly endothermic Highly endothermic
Thermodynamically Thermodynamically favored by high temperature, low pressure favored by high temperature, low pressure and high and high
number of carbons number of carbons
Kinetically favored by high temperature, high number of carbon; Kinetically favored by high temperature, high number of carbon; not not
affected by the hydrogen partial pressure affected by the hydrogen partial pressure
At the selected operating conditions, reaction is very fast and At the selected operating conditions, reaction is very fast and almost almost
total total
Cyclohexane Benzene
CH
CH
CH
CH
HC
HC
CH
2
CH
2
CH
2
H C
2
H C
2
+ 3H
2
CH
2
Desirable reactions with hydrogen production
16
Catalytic Reforming

Paraffin's Paraffin's dehydrocyclization dehydrocyclization

Multiple step reaction Multiple step reaction
Promoted by both acidic Promoted by both acidic
and metallic functions and metallic functions
Kinetically favored by Kinetically favored by high high
temperature temperature, and , and low low
pressure pressure
Dehydrogenation step Dehydrogenation step
becomes easier as paraffin becomes easier as paraffin
molecular weight increases, molecular weight increases,
but is competed but is competed
by hydro cracking by hydro cracking
At the selected operating At the selected operating
conditions, much conditions, much lower lower
rate than that of rate than that of
dehydrogenation dehydrogenation
Methylcyclohexane
CH
2
CH
2
CH CH
2
CH
3
CH
3
CH
CH
2
CH
2
CH
2
CH
2
CH
CH
3
H C
2
C H
7 16
+H
2
C H
7 14
CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
CH
3
CH
CH
3
CH
3
CH
2
CH
2
CH
2
CH
H C
2
CH
2
CH
2
CH
2
CH
2
CH
CH
3
CH
3
CH CH
CH
CH
HC
C
+3H
2
Desirable reactions with hydrogen production
17
Catalytic Reforming
Desirable reactions with hydrogen production

Linear paraffin's
Linear paraffin's
isomerization
isomerization
Promoted by the acidic function Promoted by the acidic function
Slightly exothermic Slightly exothermic
Fast Fast
Thermodynamically dependant on temperature; pressure has no Thermodynamically dependant on temperature; pressure has no
effect effect
Kinetically favored by Kinetically favored by high temperature; high temperature; not affected by the not affected by the
hydrogen partial pressure hydrogen partial pressure
C H
7 16
C H
7 16
Carbon atom Carbon atom C4 C4 C5 C5 C6 C6 C7 C7 C8 C8
% % Isoparaffin Isoparaffin at at
500 500 C C
44 44 58 58 72 72 80 80 88 88
18
Catalytic Reforming

Naphthenes
Naphthenes
isomerization
isomerization
Desirable reaction because of the subsequent dehydrogenation of Desirable reaction because of the subsequent dehydrogenation of the the
alkylcyclohexane alkylcyclohexane into an aromatic into an aromatic
Difficulty of ring rearrangement and high risk of ring opening ( Difficulty of ring rearrangement and high risk of ring opening (paraffin paraffin
formation) formation)
At the selected operating conditions, theoretically At the selected operating conditions, theoretically low rate but low rate but
subsequent dehydrogenation shifts the reaction towards the desir subsequent dehydrogenation shifts the reaction towards the desired ed
direction direction
Slightly endothermic Slightly endothermic
Easier reaction for higher carbon number Easier reaction for higher carbon number
RON RON MON MON
Ethylcyclopentane Ethylcyclopentane = = 67.2 67.2 61.2 61.2
Methylcyclohexane Methylcyclohexane = = 74.8 74.8 71.1 71.1
Toluene Toluene = = 120 120 103.5 103.5
Desirable reactions with hydrogen production
19
Catalytic Reforming
Adverse reactions

Hydrocraking
Hydrocraking
Hydrocracking Hydrocracking affects either affects either
paraffins paraffins or olefins or olefins
Promoted by both acidic Promoted by both acidic
and metallic functions and metallic functions
Favored by Favored by high temperature high temperature
and high pressure and high pressure
Exothermic Exothermic
( (risk of runaway risk of runaway reactions) reactions)
At the selected operating At the selected operating
conditions, hydro cracking conditions, hydro cracking
reaction could be complete, reaction could be complete,
but is limited by kinetics but is limited by kinetics
+H
2
C H
7 14
C H
7 16
(m)
+H
2
C H
7 14
(a)
+
C H
4 8
C H
3 8
+H
2
C H
4 10
C H
4 8
(m)
20
Catalytic Reforming

Consequences of cracking:
Consequences of cracking:

Decrease of
Decrease of
paraffins
paraffins
and increase of aromatics
and increase of aromatics
proportion (i.e. increase in octane) in the reformate
proportion (i.e. increase in octane) in the reformate
and a
and a
loss of reformate yield
loss of reformate yield

Decrease in hydrogen production
Decrease in hydrogen production
(cracking reactions
(cracking reactions
consume hydrogen)
consume hydrogen)

Increase of light ends
Increase of light ends
production and low molecular
production and low molecular
weight
weight
paraffins
paraffins
Adverse reactions
21
Catalytic Reforming
+H
2
C H
7 16
CH
4
C H
6 14
+H
2
C H
7 16
C H
2 6
C H
5 12
or
+
+

Hydrogenolysis
Hydrogenolysis

Promoted by metallic function
Promoted by metallic function

Favored by
Favored by
high temperature and high pressure
high temperature and high pressure

Exothermic (risk of runaway reactions)
Exothermic (risk of runaway reactions)
Adverse reactions
22
Catalytic Reforming

Hydrodealkylation
Hydrodealkylation
Breakage of the branched radical of an aromatic ring Breakage of the branched radical of an aromatic ring
Promoted by metallic function Promoted by metallic function
Favored by Favored by high temperature and high pressure high temperature and high pressure
Consumes hydrogen and produces methane Consumes hydrogen and produces methane
But at the selected operating conditions, and with the selected But at the selected operating conditions, and with the selected catalyst, catalyst,
this reaction is not significant this reaction is not significant
+H
2
Xylene Toluene
+CH
4
+H
2
Toluene Benzene
+CH
4
Adverse reactions
23
Catalytic Reforming

Alkylation
Alkylation

Addition of an olefin molecule on an aromatic ring
Addition of an olefin molecule on an aromatic ring

Promoted by metallic function
Promoted by metallic function

leads to heavier molecules which may
leads to heavier molecules which may
increase the
increase the
end point
end point
of the product
of the product

High tendency to
High tendency to
form coke
form coke
; must be avoided
; must be avoided
Benzene Propylene
Isopropylbenzene
HC
CH
3
+CH =CH CH
3 2
CH
3
Adverse reactions
24
Catalytic Reforming

Transalkylation
Transalkylation
(alkyl
(alkyl
disproportionation
disproportionation
)
)
Dismutation Dismutation of 2 toluene rings to produce benzene and of 2 toluene rings to produce benzene and xylene xylene
Promoted by metallic function Promoted by metallic function
Favored by Favored by very severe conditions of temperature and pressure very severe conditions of temperature and pressure
At the selected operating conditions, and with the selected At the selected operating conditions, and with the selected
catalyst, this reaction is negligible catalyst, this reaction is negligible
+
Xylene Benzene
+
Toluene
Toluene
Adverse reactions
25
Catalytic Reforming

Coking
Coking

Results from a complex group of reactions. Detailed
Results from a complex group of reactions. Detailed
mechanism not fully known yet
mechanism not fully known yet

Linked to heavy unsaturated
Linked to heavy unsaturated
products (
products (
polynuclear
polynuclear
aromatics)
aromatics)
and heavy olefins traces or
and heavy olefins traces or
diolefins
diolefins
present in the feed or in
present in the feed or in
CCR reactions
CCR reactions

Coke deposit
Coke deposit
reduces active contact area
reduces active contact area
and reduces
and reduces
catalyst activity
catalyst activity

Favored by low pressure
Favored by low pressure
In
In
Octanizing
Octanizing
operating conditions, necessity of a
operating conditions, necessity of a
continuous regeneration to maintain a low level of
continuous regeneration to maintain a low level of
coke
coke
Adverse reactions
26
Catalytic Reforming
All these reactions occur in series and parallel to each other p All these reactions occur in series and parallel to each other producing a roducing a
complicated reaction scheme complicated reaction scheme. . I In an effort to simplify the scheme n an effort to simplify the scheme
according to the reaction rates the main reactions take place in according to the reaction rates the main reactions take place in the the
following order: following order:
1st reactor 1st reactor Dehydrogenation Dehydrogenation
Isomerization Isomerization
2nd and 3rd reactors 2nd and 3rd reactors Dehydrogenation Dehydrogenation
Isomerization Isomerization
Cracking Cracking
Dehydrocyclization Dehydrocyclization
4th reactor 4th reactor Cracking Cracking
Dehydrocyclization Dehydrocyclization
Chemical reactions
27
Catalytic Reforming
Catalyst Distribution
Highly endothermic transformation
Reaction rates vary widely
The overall amount of catalyst
needed for the transformation is distributed
not equally among several adiabatic reactors
in series with intermediary heaters providing
the required heat energy input
28
Catalytic Reforming
Temperatures and Compositions
inside Reactors
T
0
T
0
- 25
T
0
- 50
R
1
R
2
R
3
A
ro
m
a
tic
s
P
a
r
a
f
f
i
n
s
Naphthenes
P
0
= 60
N
0
= 30
A
0
= 10
H1 H2 H3
R
1
R
2
R
3
Position in Reactor
Composition, Vol%
Reactor Temperature, C
29
Catalytic Reforming
The catalyst distribution is: The catalyst distribution is:

R1 R1 = = 10% 10%

R2 R2 = = 15% 15%

R3 R3 = = 25% 25%

R4 R4 = = 50% 50%
REACTIONS REACTIONS
HEAT OF HEAT OF
REACTION REACTION
(1) KCAL/MOLE (1) KCAL/MOLE
RELATIVE RATE RELATIVE RATE
(2) APPROX. (2) APPROX.
Naphthenes Naphthenes dehydrogenation dehydrogenation - - 50 50 30 30
Paraffin Paraffin dehydrocyclization dehydrocyclization - - 60 60 1 (base) 1 (base)
Isomerization Isomerization: : Paraffins Paraffins + 2 + 2
3 3
Naphthenes Naphthenes + 4 + 4
Cracking Cracking +10 +10 0.5 0.5
Chemical reactions
(1) Heat of reaction <0 =endothermic reaction.
(2) For pressure below 15 kg/cm2.
30
Catalytic Reforming
Reforming Processes
Reforming Processes
31
Catalytic Reforming
Fixed bed reformer
Feed
Separator
Recycle
Compressor
Stabilized
Reformate
1
2
3
Fuel Gas
LPG
A
B
C
Interheater 1 Interheater 2
The most frequent type of unit
Current licensors
Axens, UOP
In the old days (Chevron, Amoco, Exxon,
Engelhard)
32
Catalytic Reforming
Feed
Separator
Recycle
Compressor
Booster
Compressor
Hydrogen-
Rich Gas
Unstabilized
Reformate
Recontacting
Drum
1
2
3
Conventional Unit
33
Catalytic Reforming
Dualforming
Dualforming
Feed
Recycle
Compressor
Hydrogen
Rich
Gas
Unstabilized
Reformate
1
2
3
R
e
g
e
n
C
2
C
C
R
R
X
Booster
Compressor
Recontacting
Drum
Packinox
12b
Texicap+ RG682
Last Reactor Catalyst Continuously Regenerated
Provides excellent option for the revamp of existing SR reformers
34
Catalytic Reforming
Continuous Catalytic Regenerative
Reforming
Continuous Catalytic Regenerative
Reforming
35
Catalytic Reforming
Continuous Catalytic Regenerative
Reforming
Continuous Catalytic Regenerative
Reforming
Elutriator
Upper Hoppers
Reduction
Chamber
H
2
Lower
Hopper
Lift
Pot
Regenerator
Lock
Hopper
Upper
Surge
Drum
Reactors R1 R3 R4 R2
N
2
FC
Coke
H
2
H
2
N
2
FC
LC
FC
LC
FC
LC
LC
FC
Catalyst Continuously Regenerated
With advanced catalysts longer catalyst life and less makeup
rates possible
36
Catalytic Reforming
Objectives of Regeneration Section
Recover initial catalyst activity
Coke removal 2 Burning zones
Metal redistribution &
chloride adjustment Oxychlorination
Catalyst drying Calcination
Each zone independently optimized
37
Catalytic Reforming
RegenC
Primary
Burn
Finishing
Burn
Calcination
Oxychlor-
ination
Combustion
Gas
from Dr y Loop
Additional
Air
Chloriding
Agent
+ water
Oxychlorination
Calcination Gas
Spent Catalyst
Regener at ed Cat al yst
To Dry Burn
Loop
To Effluent
Treatment
Burning with dr y gas control:
%O
2
, temperature
Cat al yst s speci f i c
ar ea i s mai nt ai ned
Oxychlorination control:
% O
2
, temperature
and moisture
Opt i mum Pt di sper si on
38
Catalytic Reforming
RegenC Catalyst Regenerator
Combust i on
Gas Inl et
Ai r Inl et
Combust i on
Gas Out l et
Oxychl ori nat i on Out l et
Cal ci nat i on Gas
Inl et
Pri mar y Burni ng
Fi ni shi ng Burni ng
Oxychl ori nat i on
Cal ci nat i on
Chl ori di ng Agent
Inl et
Coked Cat al yst
Regenerat ed Cat al yst
39
Catalytic Reforming
Processes Variables
Processes Variables
40
Catalytic Reforming
Pressure
Temperature
Space velocity
Hydrogen partial pressure (H2/HC)
Quality of the feed
Operating Parameters Summary
41
Catalytic Reforming

Each of them
Each of them
can be fixed by the operator
can be fixed by the operator
-
-
within
within
the operating range of the equipment
the operating range of the equipment
-
-
independently from the others
independently from the others

For one set
For one set
of independent variables, for same feed
of independent variables, for same feed
characteristics, there is only
characteristics, there is only
one performance of the
one performance of the
unit
unit
i.e. one set of values for:
i.e. one set of values for:

Product yields
Product yields

Product quality (Octane)
Product quality (Octane)

Catalyst stability (coke make)
Catalyst stability (coke make)
Process variables
42
Catalytic Reforming
Pressure
43
Catalytic Reforming
Pressure

Pressure is the basic variable because of its
Pressure is the basic variable because of its
inherent
inherent
effect on reaction rates
effect on reaction rates

Effect of pressure on reactions
Effect of pressure on reactions

Low pressures enhance
Low pressures enhance
hydrogen producing
hydrogen producing
reactions:
reactions:
dehydrogenation,
dehydrogenation,
dehydrocyclisation
dehydrocyclisation
, coking
, coking

Cracking
Cracking
rate is reduced
rate is reduced
The lower the pressure, the higher the yields of
The lower the pressure, the higher the yields of
reformate and hydrogen for a given octane number.
reformate and hydrogen for a given octane number.
But high coking rate (compensated by continuous
But high coking rate (compensated by continuous
regeneration)
regeneration)
44
Catalytic Reforming
Pressure

Average catalyst pressure used, close to
Average catalyst pressure used, close to
last
last
reactor inlet pressure
reactor inlet pressure

During transient conditions (start up,
During transient conditions (start up,
shutdown, upsets) it is recommended to
shutdown, upsets) it is recommended to
increase the pressure to lower coke
increase the pressure to lower coke
formation
formation

Limits of operators action
Limits of operators action

Pressure rise limited by
Pressure rise limited by
equipments design pressure
equipments design pressure

Pressure lowering limited by
Pressure lowering limited by
recycle compressor
recycle compressor
design power and intake volume
design power and intake volume
45
Catalytic Reforming
Temperature
46
Catalytic Reforming
Temperature

Most important and
Most important and
most used
most used
operating parameter with
operating parameter with
space velocity
space velocity

Catalyst activity
Catalyst activity
is directly related to reactor temperature. By
is directly related to reactor temperature. By
simply raising or lowering reactor inlet temperatures,
simply raising or lowering reactor inlet temperatures,
operators
operators
can raise or lower product quality and yields
can raise or lower product quality and yields

It is commonly accepted to consider the weight average inlet
It is commonly accepted to consider the weight average inlet
temperature (WAIT)
temperature (WAIT)
Where Where Ti1, Ti2, Ti1, Ti2, are inlet temperature of reactors are inlet temperature of reactors
(wt of catalyst R1) (wt of catalyst R1) are weight of catalyst in reactors are weight of catalyst in reactors
( ) ( ) ( )

catalyst of wt Total
4
Ti x
4
R Catalyst wt + ....
2
Ti x
2
R Catalyst wt +
1
Ti x
1
R catalyst of wt
= WAIT
47
Catalytic Reforming

An
An
increase of temperature
increase of temperature
(i.e. WAIT) has the following
(i.e. WAIT) has the following
effects:
effects:
Increases octane Increases octane
Decreases the yield (of C5+ fraction) Decreases the yield (of C5+ fraction)
Decreases the H2 purity. Decreases the H2 purity.
Increases the coke deposit Increases the coke deposit

A
A
slight increase
slight increase
of temperature (WAIT) through the
of temperature (WAIT) through the
life of
life of
the catalyst makes up
the catalyst makes up
for this activity loss
for this activity loss

Larger and temporary changes in temperature are required:
Larger and temporary changes in temperature are required:
To change octane To change octane - - at constant feed quality and quantity at constant feed quality and quantity
To change feed quantity To change feed quantity and still maintain octane and still maintain octane
To change feed quality To change feed quality and still maintain octane and still maintain octane
Temperature
48
Catalytic Reforming
Space Velocity
49
Catalytic Reforming
Space velocity

Weight hourly space velocity:
Weight hourly space velocity:

Liquid hourly space velocity:
Liquid hourly space velocity:

Linked to residence time of feed in the reactor and
Linked to residence time of feed in the reactor and
affects the kinetics of the Reforming reactions
affects the kinetics of the Reforming reactions
reactors in catalyst of Weight
hour) (per feed of Weight
WHSV =
reactors in catalyst of Volume
hour) (per C 15 at feed of Volume
LHSV

=
Space
velocity
residence
time
higher
severity
Octane increased
Lower reformate yield
Higher coke deposit
50
Catalytic Reforming

Operators must bear in mind that
Operators must bear in mind that
each time
each time
liquid feed rate is changed, a temperature
liquid feed rate is changed, a temperature
correction must be applied
correction must be applied
if octane is to be
if octane is to be
maintained.
maintained.

Important recommendation
Important recommendation

Always decrease reactor inlet temperature first and
Always decrease reactor inlet temperature first and
decrease feed
decrease feed
flowrate
flowrate
afterwards
afterwards

Always increase feed
Always increase feed
flowrate
flowrate
first and increase
first and increase
reactor inlet temperature afterwards
reactor inlet temperature afterwards
Space velocity
51
Catalytic Reforming
Hydrogen to hydrocarbon ratio
52
Catalytic Reforming
Hydrogen to hydrocarbon ratio

H2/HC ratio
H2/HC ratio
:
:
=
=
Where Where R R is the recycle flow in Kg/h (or lb/h) is the recycle flow in Kg/h (or lb/h)
M M is the recycle gas molecular weight is the recycle gas molecular weight
F F is the feed rate in Kg/h (or lb/h) is the feed rate in Kg/h (or lb/h)
m m is the feed molecular weight is the feed molecular weight
Y Y vol. fraction of H2 in the recycle gas vol. fraction of H2 in the recycle gas

The recycle gas MW is obtained by chromatographic
The recycle gas MW is obtained by chromatographic
analysis, as well as the H2 vol. fraction (Y)
analysis, as well as the H2 vol. fraction (Y)

The feed MW is obtained by chromatographic analysis
The feed MW is obtained by chromatographic analysis
or by correlation from its distillation range and specific
or by correlation from its distillation range and specific
gravity
gravity
) (mole/hour rate flow Naphtha
recycle in ) (mole/hour hydrogen Pure
=
HC
H
2
H
2
HC
=
R
M
x Y
F
m
53
Catalytic Reforming

Operators can change the H2/HC ratio by lowering
Operators can change the H2/HC ratio by lowering
or increasing the
or increasing the
recycle compressor flow
recycle compressor flow

For a given unit, the amount of recycle is
For a given unit, the amount of recycle is
limited by
limited by
the recycle compressor
the recycle compressor
characteristics (power,
characteristics (power,
suction flow)
suction flow)

The H2/HC ratio has
The H2/HC ratio has
no obvious impact
no obvious impact
on the
on the
product quality or yield
product quality or yield

But a high H2/HC ratio
But a high H2/HC ratio
reduces the coke build up
reduces the coke build up

It is strictly recommended to operate with a H2/HC
It is strictly recommended to operate with a H2/HC
ratio equal to (or higher than) the
ratio equal to (or higher than) the
design figure
design figure
Hydrogen to hydrocarbon ratio
54
Catalytic Reforming
Feed quality
55
Catalytic Reforming
Feed quality Chemical composition

Characterization of the
Characterization of the
feedstocks
feedstocks
by:
by:

With a higher 0.85 N + A
With a higher 0.85 N + A
The same Octane content will be obtained at a lower severity The same Octane content will be obtained at a lower severity
(temperature) and the (temperature) and the product yield will be higher product yield will be higher
Or for the same severity (temperature), Or for the same severity (temperature), the Octane content will be the Octane content will be
higher higher
Higher Higher naphtenic naphtenic content. T content. The endothermic reaction heat is he endothermic reaction heat is
increased and the feed flow rate will be increased and the feed flow rate will be limited by the heater design limited by the heater design
duty duty

With lower
With lower
0.85 N + A
0.85 N + A
Higher paraffin content. Higher paraffin content. The hydrogen purity of the recycle gas The hydrogen purity of the recycle gas
decreases and operation will be decreases and operation will be limited by the recycle compressor limited by the recycle compressor
capacity capacity

Impurities
Impurities
Temporary or permanent reduction of catalyst activity by poisons Temporary or permanent reduction of catalyst activity by poisons
contained in the feed contained in the feed
0.85 N + A
56
Catalytic Reforming

The feed distillation range is generally as follows:
The feed distillation range is generally as follows:

IBP (Initial Boiling Point)
IBP (Initial Boiling Point)
70
70
-
-
100
100

C
C

EP (End Boiling Point)
EP (End Boiling Point)
150
150
-
-
180
180

C
C

Light fractions:
Light fractions:
Cyclization
Cyclization
of C6 more difficult than that of C7
of C6 more difficult than that of C7
-
-
C8
C8
The lighter the feed, the
The lighter the feed, the
higher the required
higher the required
severity
severity
for a given Octane
for a given Octane

Heavy fractions:
Heavy fractions:
high naphthenic and aromatics content
high naphthenic and aromatics content
Lower severity
Lower severity
to obtain good yields
to obtain good yields
But polycyclic compounds which favor
But polycyclic compounds which favor
coke deposit
coke deposit
Feed quality Distillation range
EP higher than 180C are generally not recommended
57
Catalytic Reforming
Operating Parameters Summary

Hereafter the theoretical effect on the unit performance of
Hereafter the theoretical effect on the unit performance of
each independent process variable taken separately
each independent process variable taken separately
:
:
Increased Increased RONC RONC Reformate yield Reformate yield Coke deposit Coke deposit
Pressure Pressure
Temperature Temperature
Space velocity Space velocity
H2/HC ratio H2/HC ratio
Naphtha Naphtha
Quality Quality
A +0.85 N A +0.85 N
End boiling point End boiling point
Initial boiling point Initial boiling point
58
Catalytic Reforming
Catalysts
Catalysts
59
Catalytic Reforming
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
Catalyst
60
Catalytic Reforming
Catalyst
Catalyst
Chlorinated gamma alumina with nanao
particle of Pt
The chlorinated gamma alumina has too
strong acid sites
The Pt promotes hydrogenolysis of
Pt
+ H2
61
Catalytic Reforming
Catalyst
In the 90s Procatalyse (now Axens)
launched promoted Pt/Re catalyst
RG 582
Then RG 682 in 2000
The promoter provides two benefits
Reduced hydrogenolysis by a modification
of the metallic cluster
Lower the number of the strongest acid
sites
62
Catalytic Reforming
Catalyst
The stability of Pt has been improved by
addition of promoters (Re, Ir)
The hydrogenolysis of Pt has been
reduced by addition of promoters
The acidity of the chlorinated gamma
alumina has been tuned by addition of
promoters
63
Catalytic Reforming
Catalyst
To improve the catalyst stability the Pt sintering has to be
hindered
Addition of promoters
Rhenium or Iridium
Explanation
Re and Ir is alloyed with Pt the boiling point of Pt is increased
Sintering reduced
Pt accessible
Pt Total
0.75
0.50
0.25
Time, hours
0 10 20 30 40 50
P
t +
R
e
P
t
1.00
Operating conditions
T = 650C
H2 = 2 000 L/kg/h
64
Catalytic Reforming
Reforming catalysts are bimetallic catalyst consisting of
platinum plus promoters on an alumina support, Rhenium and
Tin being essentially one of the promoter besides the others.
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 give the following
advantages:
o High Reformate yield
o High hydrogen yield
o High on - stream factor
o Low catalyst inventory
Catalyst
Catalyst
65
Catalytic Reforming
Catalyst
Platinum (Pt) plus other promoter(s) impregnated on to
gamma alumina containing around 1% wt chloride to
provide acidity.
Since 1967, bimetallic catalysts have been widely used.
The second metal comes from the group
Rhenium (Re)
Tin (Sn)
Iridium (Ir)
Germanium (Ge)
66
Catalytic Reforming
WHICH METAL COMBINATION TO CHOOSE
Depends on what you want from the catalyst - "THE
OBJ ECTIVES"
Stability / cycle life
Selectivity towards
hydrogen (H
2
)
liquid reformate (C
5
+ reformate)
benzene yield in C
5
+ reformate
67
Catalytic Reforming
Stability

Normal causes for catalyst ageing/deactivation
Normal causes for catalyst ageing/deactivation

metal sintering
metal sintering

temperature
temperature

metallic phase
metallic phase

presence of chloride
presence of chloride

deposition of coke on metal and acid sites
deposition of coke on metal and acid sites
Coking effect can be split
Coking effect can be split

1. Degree of poisoning of deposited coke
1. Degree of poisoning of deposited coke

2. Relative coking rate
2. Relative coking rate
68
Catalytic Reforming

Desired yields are: Desired yields are:

hydrogen hydrogen
C C
5 5
+ reformate + reformate
low benzene low benzene

Benzene Benzene
yield can be minimised by pre yield can be minimised by pre- -fractionating the fractionating the
precursors (MCP, CH, nC6P) which are present in the precursors (MCP, CH, nC6P) which are present in the
fraction boiling between 70 to 85 fraction boiling between 70 to 85 C C
benzene is also produced by the hydrodealkylation of benzene is also produced by the hydrodealkylation of
alkyl benzenes alkyl benzenes

Loss of desired yields is caused by cracking Loss of desired yields is caused by cracking
hydrocracking involving the metal plus acid sites hydrocracking involving the metal plus acid sites
hydrogenolysis involving the metal in the presence of hydrogenolysis involving the metal in the presence of
hydrogen hydrogen
SELECTI VI TY
69
Catalytic Reforming

Tin and Germanium Tin and Germanium

increases selectivity towards desired products increases selectivity towards desired products
no stability benefit no stability benefit

Rhenium and Iridium Rhenium and Iridium

increase stability increase stability
no major effect on yield selectivity no major effect on yield selectivity

Other effects such as regenerability and tolerance to feedstock Other effects such as regenerability and tolerance to feedstock
impurities has led to the PtRe combination being preferred catal impurities has led to the PtRe combination being preferred catalyst yst
SUMMARY - EFFECT OF SECOND METAL
70
Catalytic Reforming

RG 582 introduced 1994 RG 582 introduced 1994

Third metal moderates hydrogenolysis activity to Third metal moderates hydrogenolysis activity to
between that of balanced PtRe and PtSn between that of balanced PtRe and PtSn

Desired yields increased Desired yields increased

Hydrogen by 0.1 to 0.15wt% Hydrogen by 0.1 to 0.15wt%
C C
5 5
+ by around 1 wt% + by around 1 wt%

Stability studies in pilot plant show 93 Stability studies in pilot plant show 93 - - 100% of 100% of
balanced bimetallic catalyst, but in commercial units balanced bimetallic catalyst, but in commercial units
>100% is commonly seen. >100% is commonly seen.
TRI METALLIC CATALYST
71
Catalytic Reforming
Pilot test results
Low pressure pilot test
Previous Generation
- Bi-promoted catalyst
- High Pt content
Selectivity & stability improvement
Axens New series
- Multi Promoted Catalyst
- Reduced Pt content
- Tri-promoted catalyst
- Reduced Pt content
Selectivity
C5+ yield
Stability (time)
72
Catalytic Reforming
The catalyst affects reaction rates through its two different
functions/ type of sites:
o Metallic, and
o Acidic
Different types of reactions are promoted by these sites as:
o Dehydrogenation Metallic
o Dehydrocyclisation Metallic + Acidic
o Isomerisation Metallic + Acidic
o Hydrogenolysis Metallic
o Hydrocracking Metallic + Acidic
Catalysis Mechanism
Catalysis Mechanism
73
Catalytic Reforming
Catalysts Poisons
Catalysts Poisons
74
Catalytic Reforming
Temporary poisons
Which can be removed and the proper Activity and Selectivity
of catalyst is restored.
The most common temporary poisons ( inhibitors ) are:
o Sulphur
o Organic nitrogen
o Water
o Oxygenated organics
o Halogens
Catalyst Contaminants
Catalyst Contaminants
75
Catalytic Reforming
Permanent poisons
Which induce a loss of activity which can not be restored.
Catalyst Contaminants (Contd)
Catalyst Contaminants (Contd)
Main permanent poisons are
Arsenic
Lead
Copper
Iron
Nickel
Chromium
Mercury
Sodium
Potassium
76
Catalytic Reforming
Reactor Types
Reactor Types
77
Catalytic Reforming
Typical Axial Fixed-Bed
Reactors
Typical Axial Fixed-Bed
Reactors
78
Catalytic Reforming
Typical Radial Fixed-Bed
Reactor
Typical Radial Fixed-Bed
Reactor
The design of the upper part of
the reactor was made to take
into account
- density change (settling)
- possible by-passing of catalyst
- space for mechanical assembly
Bolted metal shroud and cover
Catalyst
Dead Space
79
Catalytic Reforming
Typical Radial CCR Reactor
Typical Radial CCR Reactor
Catalyst
Feed
Effluent
80
Catalytic Reforming
A New Concept of Radial Reactor
Internals
A Flexible Flow-guide that
molds to the shape of the top of the bed
Texicap
TM
Texicap
TM
81
Catalytic Reforming
Typical Radial Fixed-Bed
Reactors
Typical Radial Fixed-Bed
Reactors
The design of the upper part of
the reactor was made to take
into account
- density change (settling)
- possible by-passing of catalyst
- space for mechanical assembly
BEFORE
Bolted metal shroud and cover
Catalyst
Dead Space
82
Catalytic Reforming
Modifying Radial Fixed-Bed
Reactors with Texicap
Modifying Radial Fixed-Bed
Reactors with Texicap
Gained
with
Texicap
BEFORE AFTER
Catalyst
Dead Space
83
Catalytic Reforming
Catalyst Sampler
N
2
ATM FL
Refilling
Sampling Box
Draining
Handling Head
Receiving Pot
Drain
84
Catalytic Reforming