Axens India Private Limited

CATALYTIC REFORMING
(Private Limited Company formed under the
Companies Act, 1956)

Process,Catalysts and Reactors

on

Petroleum Federation of India

Indian Oil Corporation Ltd. (Haldia Refinery),
&
Lovraj Kumar Memorial Trust

Mohan Lal
Catalytic Reforming 1
 Introduction

World context:
High octane gasoline requirement

Catalytic Reforming 2
 Introduction

World context:

Low sulfur content,

Low benzene content,
Limited aromatics content,
Limited olefins content,
No lead

Catalytic Reforming 3
 Introduction
European Gasoline specifications trends
Ultimate
2000 2005 Soon*
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 90 60 60 50
max
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

Catalytic Reforming 4
 Introduction

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

Catalytic Reforming 5
 Introduction

New gasoline specifications require:

ƒ Maintaining a high octane level

ƒ Meeting reduced sulfur specifications

ƒ Meeting reduced Aromatics and Benzene

specifications

Catalytic Reforming 6
 Introduction

Constraints from straight run gasoline: Initial fractionation

of crude oils gives gasoline cuts with a low octane number

¾ Light gasoline (C5-C6) : RON between 60 and 70

¾ Heavy gasoline (C7-C10) : RON between 30 and 50

Refiners have to considerably improve the

quality of gasoline cuts to meet RON/MON
specifications

Catalytic Reforming 7
 Introduction

RON/MON is increased by chemical transformation

• Light gasoline : Isomerization process

n-paraffins Æ i-paraffins

Ex: n-Hexane (RON= 24.8) Æ 2,2-DM Butane (RON=

91.8)

• Heavy gasoline: Catalytic Reforming process

n-paraffins, naphtens Æ aromatics

Ex: Cyclohexane (RON = 83) Æ Benzene (RON = 108)

Catalytic Reforming 8
 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

Catalytic Reforming 9
 Fundamentals

Catalytic Reforming 10
 Purpose of reformer

Purpose of reformer
• The purpose of Reforming process is to produce :

- high octane number reformate, which is a main component for motor

fuel, aviation gasoline blending or aromatic rich feedstock.

- hydrogen rich gas

- Due to the nature of the reactions, reforming process produces also:

LPG – FG – 600 psig steam with the waste heat boilers

Catalytic Reforming 11
 Purpose of reformer

• Reformer feed is either:

- Low quality straight run naphtha
- or cracked naphtha, generally mixed with
straight run naphtha.

• 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.

Catalytic Reforming 12
 Chemical Reactions

Catalytic Reforming 13
 Chemical reactions
• Two types of reactions
involved in the Octanizing
process:
– Desirable reactions, which RON MON

lead to a higher octane

number and to high purity • Cyclohexane = 83 77.2

hydrogen production. They • Methylcyclohexane = 74.8 71.1

are the reactions to
• 1.3 dimethylcyclohexane = 71.7 71.
promote
– Adverse reactions, which • Benzene = 114.8 > 100

lead to a decrease of • Toluene = 120 103.5

octane number and a • m-Xylene = 117.5 115.
decrease in hydrogen
purity. They are the RON: Research Octane Number
reactions to minimize MON: Motor Octane Number

Catalytic Reforming 14
 Desirable reactions with hydrogen production

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

Catalytic Reforming 15
 Desirable reactions with hydrogen production

• Paraffin's dehydrocyclization
– Multiple step reaction
CH CH CH CH CH CH
– Promoted by both acidic
2 2 2 2 2
+H
2
and metallic functions CH
3
CH
2
CH
2
CH
3
CH
3 CH CH
2
CH
3

C H
– Kinetically favored by high
C H
7 16 7 14

temperature, and low

CH
pressure CH CH
CH
2 2
CH
CH
2 2
H C CH
3
– Dehydrogenation step
2
CH CH CH CH
3 2 3 CH CH
becomes easier as paraffin 2 2

molecular weight increases, Methylcyclohexane

but is competed
by hydro cracking CH
2 CH
2 CH CH
C
H C CH CH
– At the selected operating 3 HC CH + 3H
2 3 2

conditions, much lower CH

2
CH
2
CH CH
rate than that of
dehydrogenation

Catalytic Reforming 16
 Desirable reactions with hydrogen production

• Linear paraffin's isomerization

– Promoted by the acidic function
– Slightly exothermic
– Fast
– Thermodynamically dependant on temperature; pressure has no
effect
– Kinetically favored by high temperature; not affected by the
hydrogen partial pressure

C H
7 16 C H
7 16

Carbon atom C4 C5 C6 C7 C8

% Isoparaffin at
44 58 72 80 88
500°C
Catalytic Reforming 17
 Desirable reactions with hydrogen production

• Naphthenes isomerization
– Desirable reaction because of the subsequent dehydrogenation of the
alkylcyclohexane into an aromatic
– Difficulty of ring rearrangement and high risk of ring opening (paraffin
formation)
– At the selected operating conditions, theoretically low rate but
subsequent dehydrogenation shifts the reaction towards the desired
direction
– Slightly endothermic
– Easier reaction for higher carbon number
RON MON

• Ethylcyclopentane = 67.2 61.2

• Methylcyclohexane = 74.8 71.1

• Toluene = 120 103.5

Catalytic Reforming 18
 Adverse reactions

(m)

• Hydrocraking C H C H
+H
2

– Hydrocracking affects either 7 16 7 14

(a)
paraffins or olefins +H
+
2
– Promoted by both acidic
C H
7 14 C H C H
4 8 3 8

and metallic functions

(m)
– Favored by high temperature +H
2
and high pressure C H C H
4 8 4 10
– Exothermic
(risk of runaway reactions)
– At the selected operating
conditions, hydro cracking
reaction could be complete,
but is limited by kinetics

Catalytic Reforming 19
 Adverse reactions

• Consequences of cracking:

– Decrease of paraffins and increase of aromatics

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

– Decrease in hydrogen production (cracking reactions

consume hydrogen)

– Increase of light ends production and low molecular

weight paraffins

Catalytic Reforming 20
 Adverse reactions

• Hydrogenolysis
– Promoted by metallic function
– Favored by high temperature and high pressure
– Exothermic (risk of runaway reactions)

+H CH +
4
2
C H C H
7 16 6 14
or

+H C H+
2 6
C H 2
7 16 C H
5 12

Catalytic Reforming 21
 Adverse reactions

• Hydrodealkylation
– Breakage of the branched radical of an aromatic ring
– Promoted by metallic function
– 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
4
2

Xylene Toluene

+H + CH
4
2

Toluene Benzene

Catalytic Reforming 22
 Adverse reactions

• Alkylation
– Addition of an olefin molecule on an aromatic ring
– Promoted by metallic function
– leads to heavier molecules which may increase the
end point of the product
– High tendency to form coke; must be avoided

CH
3
+ CH2= CH – CH3 HC
CH
3
Benzene Propylene Isopropylbenzene

Catalytic Reforming 23
 Adverse reactions

• Transalkylation (alkyl disproportionation)

– Dismutation of 2 toluene rings to produce benzene and xylene
– Promoted by metallic function
– Favored by very severe conditions of temperature and pressure
– At the selected operating conditions, and with the selected
catalyst, this reaction is negligible

+ +

Toluene Toluene Benzene Xylene

Catalytic Reforming 24
 Adverse reactions

• Coking
– Results from a complex group of reactions. Detailed
mechanism not fully known yet
– 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
In Octanizing operating conditions, necessity of a
continuous regeneration to maintain a low level of
coke

Catalytic Reforming 25
 Chemical reactions

– All these reactions occur in series and parallel to each other producing a
complicated reaction scheme. In an effort to simplify the scheme
according to the reaction rates the main reactions take place in the
following order:

• 1st reactor Dehydrogenation

Isomerization

• 2nd and 3rd reactors Dehydrogenation

Isomerization
Cracking
Dehydrocyclization

• 4th reactor Cracking

Dehydrocyclization

Catalytic Reforming 26
 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

Catalytic Reforming 27
 Temperatures and Compositions
inside Reactors

H1 R1 H2 R2 H3 R3

Reactor Temperature, °C
T0
T0 - 25
T0 - 50

Composition, Vol%
P0 = 60
Aromatics
N0 = 30 Paraffi
ns
A0 = 10 Naphthenes
R1 R2 R3
Catalytic Reforming Position in Reactor 28
 Chemical reactions

– The catalyst distribution is:

• R1 = 10%
• R2 = 15%
• R3 = 25%
• R4 = 50%
REACTIONS HEAT OF RELATIVE RATE
REACTION (2) APPROX.
(1) KCAL/MOLE

Naphthenes dehydrogenation - 50 30

Paraffin dehydrocyclization - 60 1 (base)

Isomerization: Paraffins +2
3
Naphthenes +4

Cracking + 10 0.5

(1) Heat of reaction < 0 = endothermic reaction.

(2) For pressure below 15 kg/cm2.

Catalytic Reforming 29
 Reforming Processes

Catalytic Reforming 30
 Fixed bed reformer

• The most frequent type of unit

• Current licensors
• Axens, UOP
• In the old days (Chevron, Amoco, Exxon,
Engelhard)
Interheater 1 Interheater 2

B
1 2 3 A
Separator

Fuel Gas
Feed
LPG
Stabilized
Recycle Reformate
Compressor
C
Catalytic Reforming 31
 Conventional Unit

Booster
Compressor Hydrogen-
Rich Gas

Separator

1 2 3 Recontacting
Drum

Unstabilized
Feed Reformate

Recycle
Compressor

Catalytic Reforming 32
 Dualforming
Texicap™+ RG682 Booster Hydrogen
Compressor Rich
R Gas
e
C g
C e
R n
1 2 3 C
R 2
X 12b Recontacting
Drum

Feed Packinox
Recycle Unstabilized
Compressor Reformate

• Last Reactor Catalyst Continuously Regenerated

• Provides excellent option for the revamp of existing SR reformers

Catalytic Reforming 33
 Continuous Catalytic Regenerative
Reforming

Catalytic Reforming 34
 Continuous Catalytic Regenerative
Reforming
Upper
Elutriator Surge
Upper Hoppers Drum
LC Lock
LC
Hopper
LC
Reduction LC
Chamber
Coke

Reactors R1 R2 R3 R4 Regenerator

Lower
Hopper
H2 H2 H2 N2
FC FC FC FC N2 Lift
Pot
FC
• Catalyst Continuously Regenerated
• With advanced catalysts longer catalyst life and less makeup
rates possible
Catalytic Reforming 35
 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

Catalytic Reforming 36
 RegenC

Spent C atalyst
Burning with dry gas control:
C om bustion Prim ary % O 2 , tem perature
G as Burn
from D ry Loop
Catalyst’s specific
Additional area is m aintained
Finishing T o D ry Burn
Air Loop
Burn

O xychlor- T o Effluent O xychlorination control:

ination T reatm ent
Chloriding % O 2 , tem perature
Agent and m oisture
+ water
C alcination
O xychlorination O ptim um Pt dispersion
C alcination G as
R egen erated C atalyst

Catalytic Reforming 37
 RegenC Catalyst Regenerator

«Coked» Catalyst

Com bustion
Gas Inlet

Primary Burning

Air Inlet

Finishing Burning
Combustion
Gas Outlet

Oxychlorination Outlet
Oxychlorination
Chloriding Agent
Inlet
Calcination

Calcination Gas
Inlet Regenerated Catalyst

Catalytic Reforming 38
 Processes Variables

Catalytic Reforming 39
 • Pressure
• Temperature
• Space velocity
• Hydrogen partial pressure (H2/HC)
• Quality of the feed
• Operating Parameters Summary

Catalytic Reforming 40
 Process variables

• Each of them can be fixed by the operator - within

the operating range of the equipment -
independently from the others

• For one set of independent variables, for same feed

characteristics, there is only one performance of the
unit i.e. one set of values for:
– Product yields
– Product quality (Octane)
– Catalyst stability (coke make)

Catalytic Reforming 41
 Pressure

Catalytic Reforming 42
 Pressure

• Pressure is the basic variable because of its

inherent effect on reaction rates
• Effect of pressure on reactions
– Low pressures enhance hydrogen producing reactions:
dehydrogenation, dehydrocyclisation, coking
– Cracking rate is reduced

The lower the pressure, the higher the yields of

reformate and hydrogen for a given octane number.
But high coking rate (compensated by continuous
regeneration)

Catalytic Reforming 43
 Pressure

• Average catalyst pressure used, close to last

reactor inlet pressure
• During transient conditions (start up,
shutdown, upsets) it is recommended to
increase the pressure to lower coke
formation
• Limits of operators action
– Pressure rise limited by equipments design pressure

– Pressure lowering limited by recycle compressor

design power and intake volume
Catalytic Reforming 44
 Temperature

Catalytic Reforming 45
 Temperature

• Most important and most used operating parameter with

space velocity

• Catalyst activity is directly related to reactor temperature. By

simply raising or lowering reactor inlet temperatures, operators
can raise or lower product quality and yields

• It is commonly accepted to consider the weight average inlet

temperature (WAIT)

(wt of catalyst R1 x Ti1) + (wt Catalyst R 2 ) x Ti2.... + (wt Catalyst R4 ) x Ti4

WAIT =
Total wt of catalyst

Where Ti1, Ti2, … are inlet temperature of reactors

(wt of catalyst R1)… are weight of catalyst in reactors

Catalytic Reforming 46
 Temperature
• An increase of temperature (i.e. WAIT) has the following
effects:
– Increases octane
– Decreases the yield (of C5+ fraction)
– Decreases the H2 purity.
– Increases the coke deposit

• A slight increase of temperature (WAIT) through the life of

the catalyst makes up for this activity loss

• Larger and temporary changes in temperature are required:

– To change octane - at constant feed quality and quantity
– To change feed quantity and still maintain octane
– To change feed quality and still maintain octane

Catalytic Reforming 47
 Space Velocity

Catalytic Reforming 48
 Space velocity

• Weight hourly space velocity: WHSV = Weight of feed (per hour)

Weight of catalyst in reactors

• Liquid hourly space velocity: LHSV =

Volume of feed at 15°C (per hour)
Volume of catalyst in reactors

• Linked to residence time of feed in the reactor and

affects the kinetics of the Reforming reactions

higher Octane increased

Space residence
severity Lower reformate yield
velocity time
Higher coke deposit

Catalytic Reforming 49
 Space velocity

• Operators must bear in mind that each time

liquid feed rate is changed, a temperature
correction must be applied if octane is to be
maintained.

• Important recommendation
– Always decrease reactor inlet temperature first and
decrease feed flowrate afterwards
– Always increase feed flowrate first and increase
reactor inlet temperature afterwards

Catalytic Reforming 50
 Hydrogen to hydrocarbon ratio

Catalytic Reforming 51
 Hydrogen to hydrocarbon ratio

R
H2 Pure hydrogen (mole/hour ) in recycle H2 M xY
• H2/HC ratio: HC
=
Naphtha flow rate (mole/hour )
= HC = F
m

Where R is the recycle flow in Kg/h (or lb/h)

M is the recycle gas molecular weight
F is the feed rate in Kg/h (or lb/h)
m is the feed molecular weight
Y vol. fraction of H2 in the recycle gas

• The recycle gas MW is obtained by chromatographic

analysis, as well as the H2 vol. fraction (Y)

• The feed MW is obtained by chromatographic analysis

or by correlation from its distillation range and specific
gravity

Catalytic Reforming 52
 Hydrogen to hydrocarbon ratio

• Operators can change the H2/HC ratio by lowering

or increasing the recycle compressor flow

• For a given unit, the amount of recycle is limited by

the recycle compressor characteristics (power,
suction flow)

• The H2/HC ratio has no obvious impact on the

product quality or yield

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

• It is strictly recommended to operate with a H2/HC

ratio equal to (or higher than) the design figure
Catalytic Reforming 53
 Feed quality

Catalytic Reforming 54
 Feed quality Chemical composition

• Characterization of the feedstocks by: 0.85 N + A

• With a higher 0.85 N + A
– The same Octane content will be obtained at a lower severity
(temperature) and the product yield will be higher
– Or for the same severity (temperature), the Octane content will be
higher
– Higher naphtenic content. The endothermic reaction heat is
increased and the feed flow rate will be limited by the heater design
duty
• With lower 0.85 N + A
– Higher paraffin content. The hydrogen purity of the recycle gas
decreases and operation will be limited by the recycle compressor
capacity

• Impurities
– Temporary or permanent reduction of catalyst activity by poisons
contained in the feed
Catalytic Reforming 55
 Feed quality Distillation range

• The feed distillation range is generally as follows:

• IBP (Initial Boiling Point) 70-100 °C
• EP (End Boiling Point) 150-180 °C
• Light fractions:
Cyclization of C6 more difficult than that of C7-C8
The lighter the feed, the higher the required
severity for a given Octane
• Heavy fractions:
high naphthenic and aromatics content
Lower severity to obtain good yields
But polycyclic compounds which favor coke deposit
EP higher than 180°C are generally not recommended
Catalytic Reforming 56
 Operating Parameters Summary

• Hereafter the theoretical effect on the unit performance of

each independent process variable taken separately:
Increased RONC Reformate yield Coke deposit

Pressure

Temperature

Space velocity

H2/HC ratio

A + 0.85 N

Naphtha
End boiling point
Quality

Initial boiling point

Catalytic Reforming 57
 Catalysts

Catalytic Reforming 58
 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.

Catalytic Reforming 59
 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

Catalytic Reforming 60
 Catalyst

• In the 90’s 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

Catalytic Reforming 61
 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

Catalytic Reforming 62
 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 Î the “boiling point” of Pt is increased
Î Sintering reduced
1.00

0.75 Pt + Re
Pt accessible
Pt Total
0.50 Pt
• Operating conditions
• T = 650°C
• H2 = 2 000 L/kg/h 0.25
0 10 20 30 40 50
Catalytic Reforming Time, hours 63
 Catalyst
• 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

Catalytic Reforming 64
 Catalyst

¾Platinum (Pt) plus other promoter(s) impregnated on to

gamma alumina containing around 1% wt chloride to
provide acidity.

¾Since 1967, bimetallic catalysts have been widely used.

¾The second metal comes from the group

ŽRhenium (Re)
ŽTin (Sn)
ŽIridium (Ir)
ŽGermanium (Ge)

Catalytic Reforming 65
 WHICH METAL COMBINATION TO CHOOSE

¾Depends on what you want from the catalyst - "THE

OBJECTIVES"

¾Stability / cycle life

¾Selectivity towards
Žhydrogen (H2)
Žliquid reformate (C5+ reformate)
Žbenzene yield in C5+ reformate

Catalytic Reforming 66
 Stability

• Normal causes for catalyst ageing/deactivation

– metal sintering
– temperature
– metallic phase
– presence of chloride

– deposition of coke on metal and acid sites

Coking effect can be split
– 1. Degree of poisoning of deposited coke
– 2. Relative coking rate

Catalytic Reforming 67
 SELECTIVITY

• Desired yields are:

– hydrogen
– C5+ reformate
– low benzene
• Benzene
– yield can be minimised by pre-fractionating the
precursors (MCP, CH, nC6P) which are present in the
fraction boiling between 70 to 85°C
– benzene is also produced by the hydrodealkylation of
alkyl benzenes

• Loss of desired yields is caused by cracking

– hydrocracking involving the metal plus acid sites
– hydrogenolysis involving the metal in the presence of
hydrogen

Catalytic Reforming 68
 SUMMARY - EFFECT OF SECOND METAL

• Tin and Germanium

– increases selectivity towards desired products
– no stability benefit

• Rhenium and Iridium

– increase stability
– no major effect on yield selectivity

• Other effects such as regenerability and tolerance to feedstock

impurities has led to the PtRe combination being preferred catalyst

Catalytic Reforming 69
 TRI METALLIC CATALYST

• RG 582 introduced 1994

• Third metal moderates hydrogenolysis activity to
between that of balanced PtRe and PtSn
• Desired yields increased
– Hydrogen by 0.1 to 0.15wt%
– C5+ by around 1 wt%
• Stability studies in pilot plant show 93 - 100% of
balanced bimetallic catalyst, but in commercial units
>100% is commonly seen.

Catalytic Reforming 70
 Pilot test results
Low pressure pilot test

Axens New series

Selectivity
- Multi Promoted Catalyst
C5+ yield - Reduced Pt content

Previous Generation
- Bi-promoted catalyst
- High Pt content
- Tri-promoted catalyst
- Reduced Pt content

Stability (time)
Selectivity & stability improvement

Catalytic Reforming 71
 Catalysis Mechanism

• 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

Catalytic Reforming 72
 Catalysts Poisons

Catalytic Reforming 73
 Catalyst Contaminants

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

Catalytic Reforming 74
 Catalyst Contaminants (Contd…)

Permanent poisons –
Which induce a loss of activity which can not be restored.

Main permanent poisons are

• Arsenic
• Lead
• Copper
• Iron
• Nickel
• Chromium
• Mercury
• Sodium
• Potassium

Catalytic Reforming 75
 Reactor Types

Catalytic Reforming 76
 Typical Axial Fixed-Bed
Reactors

Catalytic Reforming 77
 Typical Radial Fixed-Bed
Reactor
Bolted metal shroud and cover

The design of the upper part of

the reactor was made to take
Catalyst into account
Dead Space
- density change (settling)
- possible by-passing of catalyst
- space for mechanical assembly

Catalytic Reforming 78
 Typical Radial CCR Reactor

Feed
Catalyst

Effluent

Catalytic Reforming 79
 Texicap TM

A New Concept of Radial Reactor

Internals

A Flexible Flow-guide that

molds to the shape of the top of the bed

Catalytic Reforming 80
 Typical Radial Fixed-Bed
Reactors
BEFORE
Bolted metal shroud and cover

The design of the upper part of

the reactor was made to take
Catalyst into account
Dead Space
- density change (settling)
- possible by-passing of catalyst
- space for mechanical assembly

Catalytic Reforming 81
 Modifying Radial Fixed-Bed
Reactors with Texicap

Catalyst BEFORE AFTER

Dead Space

Gained
with
Texicap

Catalytic Reforming 82
 Catalyst Sampler

Refilling
Sampling Box

Draining
N2 ATM FL

Handling Head

Receiving Pot

Drain
Catalytic Reforming 83
Catalytic Reforming 84