Chapter 1: Catalytic Reforming

1. Catalytic Reforming
1.1 Objectives of Catalytic Reforming
• To improve the octane number of gasoline by converting naphthas (a light hydrocarbon
fraction obtained from atmospheric distillation) into higher-performance fuels for
engines.
• To produce hydrogen: the process generates hydrogen as a by-product, which is used in
other refining processes such as hydrotreating.
• To manufacture feedstocks for petrochemistry: the reforming products, such as benzene,
toluene, and xylenes (BTX), are important raw materials for the petrochemical industry.
1.2. Gasoline
Gasoline is a flammable liquid derived from petroleum distillation. It is a complex mixture of
numerous chemical species, including alkanes, alkenes, aromatic hydrocarbons (C7, C8, and
C9), as well as several other compounds. Gasoline is primarily used as a fuel in internal
combustion engines, such as spark-ignition engines (a type of combustion engine in which the
thermal energy released during combustion is converted into mechanical energy within the
engine).
As a fuel, gasoline has a tendency toward auto-ignition; therefore, its resistance to this
phenomenon is measured by the octane rating, which indicates the fuel’s resistance to premature
ignition.
Gasolines obtained by simple distillation of crude oils within the temperature range specified
by these standards are insufficient in both quantity and quality. Various refining units make it
possible to produce gasoline either from heavy fractions through cracking, or from light
fractions through polymerization or alkylation. The improvement of the quality of the heavy
gasoline fraction, or of gasoline originating from another unit, is achieved mainly through
catalytic reforming.
Catalytic reforming aims to convert naphthenic constituents (with a low octane number) into
aromatic constituents with a high octane number. (It transforms naphthenic products into
aromatics).
1.2.1. Octane Number (ON)

The octane number measures the resistance of a fuel (gasoline) to auto-ignition or detonation
in the engine. More simply, it represents the fuel’s ability to ignite without the intervention of
the spark plug. The octane number expresses the proportion of octane relative to heptane. The
higher this ratio, the greater the resistance to auto-ignition, ensuring better engine performance.
It should be noted, however, that the octane number is defined on a scale between 0 and 100,
corresponding respectively to heptane and iso-octane. Example:
 Unleaded 95, which has an octane number of 95 and consists of 95% octane and 5%
heptane.
 Unleaded 98, which has an octane number of 98 and therefore contains 98% octane and
2% heptane. It is therefore preferable to use SP98 (a fuel with a higher octane number).
-The reforming unit essentially consists of a series of three reactors containing catalyst and a
fractionator used to separate the different products at the outlet of the reactors. This catalyst is
highly sensitive to the presence of sulfur- and nitrogen-containing compounds; therefore, the
reforming feed must be free of sulfur, nitrogen, and their derivatives.
-The reaction takes place under high pressure and at high temperature (around 550 °C), with
the production of hydrogen originating from naphthenic molecules. It is an endothermic
reaction: the bonds within the naphthenic molecules break, releasing hydrogen, and these
molecules give rise to aromatic compounds, the main representative of which is benzene (C₆H₆).

-At the outlet of the reactors, after passing through a separation unit, the stream contains:
 Hydrogen
 Fuel gas (methane and ethane)
 Propane
 Butane
 Reformate
 Hydrogen is used in hydrotreating and hydrodesulfurization.
 Fuel gas is directed to the fuel gas network.
 Propane and butane are sent to a storage vessel.
Finally, reformate is blended with light naphtha and butane in defined proportions to produce
regular and premium gasoline. Through a fractionation process of the reformate, BTX aromatics
(benzene, toluene, and xylene), which are highly sought after in the petrochemical industry, are
obtained.
-The Feed

The feed to the unit may come from different sources, such as heavy naphtha from atmospheric
distillation after hydrotreating, or from the hydrocracker. Catalytic reforming feeds are derived
from the atmospheric distillation of crude oil. They consist mainly of paraffins and cycloalkanes
containing 6 to 10 carbon atoms. Their octane number ranges between 30 and 65, depending
on the content of cycloalkanes, paraffins, and aromatic compounds. They contain between 350
and 500 ppm of sulfur, depending on the nature of the crude.

1.3. Reactions Involved

The chemical reactions taking place during catalytic reforming are numerous (dehydrogenation,
dehydrocyclization, isomerization, etc.). All of these reactions require a temperature of around
500 °C. The catalysts used are typically platinum supported on alumina.
Dehydrogenation reactions of paraffins or cycloalkanes, producing respectively one mole of
olefin and one mole of hydrogen, or one mole of aromatic compound and three moles of H₂.
a) Dehydrogenation of Paraffins
Example: n-Hexane → 1-Hexene + H₂
CH3–CH2–CH2–CH2–CH2–CH3 → CH2=CH–CH2–CH2–CH2–CH3 + H2
A straight-chain alkane loses two hydrogens to form a double bond (alkene).
b) Dehydrogenation of Cycloalkanes
Example: Cyclohexane → Benzene + 3 H₂
The six-membered saturated ring (cyclohexane) becomes benzene, an aromatic ring with three
conjugated double bonds.

c) Isomerization reactions of alkylcyclopentanes into alkylcyclohexanes, which, upon

dehydrogenation, yield the corresponding aromatic compound along with the production of
three moles of H₂.
Example: Methylcyclopentane → Cyclohexane → Benzene + 3 H₂
→ → +3 H₂

(Methylcyclopentane can be converted to cyclohexane through a catalytic isomerization

reaction (rearrangement) that expands the 5-membered ring to a 6-membered ring.
Step 1: Isomerization
Methylcyclopentane → Cyclohexane
Step 2 : Dehydrogenation
Cyclohexane → Benzene + 3 H₂

d) Dehydrocyclization reactions of paraffins into aromatics with the production of four

moles of H₂. Dehydrocyclization = Cyclization (ring formation) + Dehydrogenation (loss
of H₂) Example: n-Heptane → Toluene + 4 H₂ ( heptane (a straight-chain alkane) is
converted into toluene (an aromatic compound) with the release of four molecules of
hydrogen gas.)

Step 1: Cyclization
• The linear chain of n-heptane (C₇H₁₆) undergoes intramolecular rearrangement.
• A bond forms between the first and sixth carbon atoms, creating a six-membered
ring and leaving one –CH₃ (methyl) group attached to the ring.
• This gives a methylcyclohexane intermediate.

Step 2: Dehydrogenation
• The methylcyclohexane then loses six hydrogen atoms (3 H₂) to form toluene
(C₆H₅–CH₃), an aromatic compound.
• The Pt/Al₂O₃ catalyst promotes this step efficiently at ≈ 500 °C.

→ + 3H2
e) Isomerization reactions of paraffins into isoparaffins.
Example: n-Pentane → Isopentane (2-Methylbutane)
CH3–CH2–CH2–CH2–CH3 → CH3–CH(CH3)–CH2–CH3
Straight-chain → branched-chain hydrocarbon.
 Reactions 1, 2, and 5 are highly endothermic reactions (ΔH = +209 and +260 kJ/mol,
respectively). They are therefore thermodynamically favored at high temperature and low
pressure.
 Reactions 3 and 4 are slightly exothermic (ΔH = –10 kJ/mol) at low temperature, and
independent of pressure.

 The activation of catalysts is achieved by catalysts capable of promoting isomerization

and cyclization as well as dehydrogenation. In this context, the catalytic systems
employed are multifunctional: bifunctional.
 A hydrogenation–dehydrogenation–hydrogenation function: provided by the presence
of a metal (this element must be active and stable at temperatures around 500 °C), and its
content must be carefully controlled to minimize undesirable side reactions leading to the
production of light hydrocarbons (such as methane).
 An acid function: provided by the support, with or without the addition of a halogenated
compound, which promotes to varying degrees the reactions of isomerization and
cyclization. The acidity must be controlled to limit hydrocracking.
1.4 Catalyst Development:
The first catalytic reforming catalyst was platinum on chlorinated alumina, developed in
1949. Platinum provides the metallic function, while alumina chlorinated with 1 wt.%
chlorine ensures the acidic function.
The catalysts are manufactured in the form of beads or extrudates with a diameter ranging
from 1.2 to 2.2 mm.
Industrial requirements for the catalyst
The required qualities are as follows:
• High activity, allowing acceptable conversion rates to be achieved under the most
economical conditions possible (low pressure, low temperature).
• Good selectivity, ensuring high yields of the desired product while limiting side
reactions.
• Mechanical strength.
• Cost-effectiveness (relatively inexpensive).
• Good reproducibility in preparation.
• High stability, evolving only very slowly over time. Compared to other industrial
catalysts, the reforming catalyst presents a number of particular characteristics related
to its nature, its use, and its cost.
• Its properties must be compatible with its operating conditions.
• They must not be degraded by temperatures that can reach 550 °C.
• The catalyst must be regenerable, in order to minimize downtime.
• The platinum contained in the catalyst is recovered and reused.
• Other properties such as:
Morphology: The external morphology of the catalytic particles must be adapted to
the corresponding catalytic process.
• For moving beds, catalysts are prepared in the form of spherical powders to minimize
attrition and abrasion problems.

• For fluidized beds, powders are preferably spheroidal in shape in order to reduce
attrition.

• For fixed beds, catalysts are used in the form of beads, rings, or extruded pellets.
 Mechanical Strength:
Good mechanical strength prevents catalyst fouling caused by its own weight and by the
various mechanical stresses resulting from transfer between the reactor and the
regenerator. The catalyst must be sufficiently robust to avoid breakage or attrition during
its transfer between the reactors and the regenerator in a Continuous Catalytic
Regeneration (CCR) process.
 Mechanical Strength:
Good mechanical strength prevents catalyst fouling caused by its own weight and by the
various mechanical stresses resulting from transfer between the reactor and the
regenerator. The catalyst must be sufficiently robust to avoid breakage or attrition during
its transfer between the reactors and the regenerator in a Continuous Catalytic
Regeneration (CCR) process.

During the start-up of a catalytic reforming unit, it is essential to take several

precautions in order to ensure optimal use of the catalyst and to avoid incidents. The
main steps and precautions to be followed are as follows:
1-Pre-startup checks:
• Equipment inspection: Ensure that all equipment
(columns, reactors, compressors, etc.) is in good operating
condition and properly purged.
• Leak control: Verify the tightness of the system to prevent any leakage of
hydrocarbon gases, hydrogen, or other chemicals.
• Instrument verification: Calibrate and test control and safety instruments
(temperature sensors, pressure sensors, safety valves).
• Circuit purification: Use nitrogen to purge the lines and eliminate residual oxygen in
order to prevent explosion or fire hazards when introducing gases.
2-Catalyst Heating-Up
• Progressive temperature rise: The temperature increase must be carried out
gradually in order to avoid damaging the catalyst. Excessive heating may cause cracks
in the catalyst support and lead to a loss of active surface area.
• Monitoring of critical parameters: It is essential to monitor temperature, pressure,
and hydrogen flow to prevent overheating or premature deactivation of the catalyst.
• Hydrogen inerting: Before the introduction of hydrocarbons, the unit is often
pressurized with hydrogen to protect the catalyst from oxidation.
3-Smooth Process Start-Up
• Gradual introduction of hydrocarbons: Start with light feeds containing minimal
sulfur concentration to avoid catalyst poisoning. The flow rate should be increased
progressively while monitoring catalyst activity:
 The feedstock (naphtha) must be introduced slowly and carefully into the reactor
after it has been filled with hydrogen and heated to the desired temperature.
 The feed flow rate is gradually increased while carefully monitoring:
• Reactor temperature,
• Hydrogen-to-hydrocarbon ratio,
• Catalyst performance (to detect any sign of deactivation or coking).
• Adjust temperature, pressure, and flow conditions to optimize reforming reactions
(isomerization, dehydrogenation, cyclization).
4. Control of Fouling and Poisoning
• Monitoring of contaminants: Contaminants such as sulfur, nitrogen, heavy metals,
and water can deactivate the catalyst. Regular monitoring of impurity levels is
essential.
 • Regeneration management: When catalyst performance decreases, regeneration
must be carried out in a controlled manner, either through controlled combustion of
coke deposits or by chemical washing, depending on the type of contamination.
5-Incident Management
• Monitoring of temperature excursions: Excessive temperatures can cause rapid
catalyst degradation and create hot spots, threatening the integrity of the equipment:
• In catalytic reforming, maintaining a stable temperature is critical.
• If the temperature rises excessively, it may:
• Cause catalyst sintering → loss of surface area and active sites,
• Create local hot spots that can damage the reactor tubes or catalyst bed,
• Accelerate undesirable side reactions (coke or methane formation).
• Continuous temperature monitoring across the reactor beds is essential to detect and
correct any deviation early.
• Emergency shutdown: In case of emergency (fire, leakage, equipment failure), the unit
must be capable of being safely shut down. Protection systems, such as relief valves
and depressurization systems, must be fully operational.
 Relief valves → soupapes de sûreté qui s’ouvrent automatiquement quand la pression
devient trop élevée.
 Depressurization systems (ou blowdown systems) → dispositifs permettant de relâcher
rapidement la pression du réacteur en envoyant les gaz vers une torche.
 Ces systèmes doivent être entièrement fonctionnels pour éviter toute explosion ou
surpression pendant un arrêt d’urgence
• Overheating and coke formation: Overheating can lead to excessive coke deposition
on the catalyst, thereby reducing its efficiency. Constant monitoring of temperature
and gas flow is required to prevent this issue.

6. Optimization of Catalyst Lifetime

-Regeneration Cycle Management:
A rigorous control of regeneration cycles is essential to maximize catalyst longevity and
preserve its catalytic efficiency over extended operating periods. Proper regeneration
scheduling prevents irreversible deactivation and ensures stable activity throughout the
process.
-Contamination Reduction:
Maintaining feedstock purity and ensuring the use of high-quality hydrogen gas with minimal
impurity levels are key factors in reducing catalyst contamination. Such precautions
significantly contribute to prolonging the catalyst’s operational life and maintaining consistent
performance.
-Operating Parameter Monitoring:
Continuous and precise monitoring of critical operating variables—such as temperature,
pressure, and flow rate—ensures that the catalyst remains within its optimal activity window.
This operational stability minimizes thermal and mechanical stress, thereby enhancing both
efficiency and durability.
By following these precautions and closely monitoring the start-up process, it is possible to
maximize the performance and longevity of the catalyst in a catalytic reforming unit, while
minimizing the risk of incidents.
Main Steps of the Process
Catalytic reforming consists of several key stages that take place in a series of reactors
containing the catalyst:
1. Feedstock Pretreatment (Naphtha):
The naphtha feed is hydrotreated prior to entering the reformer in order to remove
impurities such as sulfur, nitrogen, and metals, which could otherwise poison the catalyst.
2. Hydrogen Compression:
Hydrogen plays a crucial role in the catalytic reforming process. It is recycled within the
unit and mixed with the naphtha feed before entering the reactors.
The hydrogen produced in the unit is compressed and combined with the hydrocarbon
stream to prevent coke formation and to protect the catalyst.
3. Reforming Reactors:
The process takes place in a series of reactors packed with catalyst, where the main
reforming reactions occur.
The reactors operate at high temperatures (450–520 °C) and moderate pressures (5–45
bar).
Main Reactions
Dehydrogenation:Naphthenes (cyclic hydrocarbons) are converted into
aromatics with the release of hydrogen.
Isomerization:Linear alkanes are converted into branched alkanes, which
exhibit a higher octane number.
 Cyclization:Linear hydrocarbons are cyclized to form naphthenes or
aromatics.
Each reactor contributes to maximizing the conversion of hydrocarbons into high-value
products.
4. Product Recovery (Cooling Unit)
After each reactor, the products are cooled before being sent either to the next reactor or to the
separation stage. The cooling process enables the recovery of gases and liquids under optimal
conditions for efficient separation.
5. Reformate Separation (Stabilizer Column)
After passing through the reactors, the products are directed to a stabilizer column, where the
reformate — the final liquid product containing high-quality gasoline — is separated from the
lighter gases.
This column separates the various components based on their boiling points.
6. Hydrogen Recycling (Hydrogen Recycle)
The hydrogen generated during the reforming reactions is largely recycled within the system.
A portion of this hydrogen can also be recovered for use in other refinery units, such as
hydrotreating or hydrocracking.
Recycling hydrogen ensures sufficient pressure in the reactors and minimizes coke formation
on the catalyst surface.
7. Final Products
-Reformate:
The liquid product obtained contains high-octane gasoline, which is used in the formulation of
motor fuels.
-Hydrogen Gas:
A significant portion of the hydrogen produced is recovered and reused in other refinery
processes.
-Bimetallic Catalysts
The most recent reforming catalysts are bimetallic. The second metal plays several important
roles: it stabilizes the dispersion state of platinum, decreases the rate of coke formation, and
modifies the reaction selectivity, allowing operation at lower pressures where the formation of
aromatic compounds is favored.
These catalysts consist of platinum combined with another metal such as iridium, rhenium,
tin, or germanium. They have made it possible—while maintaining acceptable cycle
lengths—to either increase catalytic activity under identical operating conditions (Ir), lower
the operating pressure while maintaining the same cycle length (Re), or improve yields at low
pressure (Ge, now seldom used).
By adjusting the relative concentrations of these metals, the catalytic properties can be
optimized to meet the specific operating conditions of the reforming unit.
Table: Typical Second Metal Loadings
Deuxième métal Concentrations(%masse)
Iridium 0.02 à 0.20
Rhénium 0.20-0.60
Etain 0.05-0.50
Tableau : Les principales caractéristiques du catalyseur Pt/Al2O3/Cl.
Caractéristiques Valeurs moyennes
Support Alumine γ cubique
Impuretés : < 500
Alcalins + alcalinoterreux + fer (ppm)
Surface spécifique (m2/g )Methode BET 150-250
Volume poreux total ( cm3/g )Methode 0.5-0.8
"t"oumethodeDubinin
Diamètre des pores ( nm )Loi de Kelvin 8-10
Teneur en chlore ( % masse ) 1
Teneur en Platine ( % masse ) 0.2-0.6
Diamètre des extrudés ou billes ( nm 1.2-2.2
)Porisimètre à mercure
 Pt/(γ-Al₂O₃–Cl) Catalyst
The first catalyst developed was a monometallic platinum catalyst supported on alumina, used
in the semi-regenerative reforming (SR) process.
This type of catalyst is prepared by impregnating metallic precursors onto the support. The
impregnation technique itself has evolved significantly over the years, allowing for high
dispersion of the active phase.
This type of catalyst was soon complemented by a bimetallic Pt–Re catalyst in order to reduce
the rapid deactivation caused by slight sintering of the metallic phase and, more importantly,
by heavy coke deposition.
  Pt–Re/γ-Al₂O₃–Cl Catalyst
Rhenium has the advantage of stabilizing the metallic phase, making it more resistant to coke
deposition and thereby extending its lifetime. Rhenium promotes the hydrogenation of
hydrocarbon species adsorbed on the catalyst surface, including those responsible for coke
formation, thus minimizing its occurrence.
However, rhenium also exhibits a non-negligible hydrogenolysis activity. Therefore, the
catalyst must undergo a rhenium passivation step through sulfidation.
A catalyst with a higher Re-to-Pt ratio is generally more effective for processing heavy
naphtha feeds (predominantly containing hydrocarbons with more than eight carbon atoms,
>C₈).
 PtSn/γ-Al₂O₃–Cl Catalyst
The PtSn catalyst is commonly used in the CCR (Continuous Catalytic Reforming)
process.
The addition of tin (Sn) enhances the selectivity of the catalyst and reduces the sintering of
the metallic phase during the repeated regeneration cycles inherent to the process design.
Tin is known to inhibit strong acid sites present on alumina, thereby reducing hydrocarbon
cracking but also slightly decreasing the overall catalytic activity .
Sintering refers to a thermal degradation process that leads to the loss of active surface area
due to particle growth or metal evaporation.
It can occur either gradually or as a sudden, extensive phenomenon, and is generally
irreversible and non-regenerable.
1-Deactivation by Poisoning of the Metallic Function
-The presence of hydrogen sulfide (H₂S) poisons platinum by reversible adsorption, according
to the following equilibrium reaction:
Pt+H2S⇌PtS+H2
-Coke formation during the reaction blocks the active metallic sites and reduces catalytic
activity.
-Metals and metalloids present in the feed can also inhibit the activity of platinum by forming
inactive compounds or by blocking surface sites.
2. Deactivation by Poisoning of the Support
Catalyst supports exhibiting acidic functions (such as alumina or zeolites) can be inhibited by
basic compounds, such as water or ammonia, which neutralize the acid sites and consequently
decrease the catalytic activity.
3-Deactivation Due to Physical Causes
1. Mechanical Damage
 Wear: deterioration resulting from prolonged use.
 Abrasion: wear caused by friction between particles, leading to loss of catalyst
material.
 Loss of specific surface area due to crushing or mechanical stress.
Such damage can occur during transportation, storage, packaging, or operation,
particularly in the following situations:
 During reactor loading and unloading (filling and emptying operations).
 Inside the reactor: due to the weight of the catalyst bed (in fixed-bed systems).
 In moving systems: such as fluidized beds, where particle–particle and particle–wall
collisions cause erosion and attrition.
2. During Process Start-up and Shutdown
 Thermal shocks: caused by rapid temperature variations.
 Chemical transformations: such as sulfidation during activation stages.
 Regeneration steps: involving high temperatures and steam, which can alter catalyst
texture or cause sintering.
3. Corrosion and Dissolution: dissolution of the catalyst in the reaction medium.
 Alumina supports, for example, are susceptible to dissolution at pH > 12 or pH < 3.
 Metal oxides may also undergo sulfidation in the presence of H₂S, leading to loss of
catalytic activity.
4-Catalyst deactivation by sintering
Catalyst deactivation is generally associated with a loss of acidity caused by coke deposition
and chlorine elution, as well as with a decrease in accessible metallic surface area due to
sintering and additional carbon deposition.
Sintering is a thermal degradation process that results in the loss of active surface area and, in
some cases, metal evaporation.
It can occur either gradually or as a sudden and extensive phenomenon, and is typically
irreversible and non-regenerable.
5-Coke Formation
The coke formed represents a condensed form of the initial hydrocarbon molecules. It is a solid
material, rich in carbon and poor in hydrogen, produced through a series of successive reactions
such as alkylation, cyclization, and dehydrogenation.
For example, coke can be generated through a sequence of dehydrocyclization reactions,
leading to the formation of heavy, condensed polyaromatic species with a graphitic structure.
These polycondensed aromatic compounds may originate from alkylaromatics or from highly
unsaturated molecules such as diolefins.
Coke formation is favored by high temperatures and low pressures, which promote the
condensation and polymerization of hydrocarbon intermediates on the catalyst surface.
6-Catalyst deactivation by fouling
-Fouling refers to the occurrence of secondary reactions involving reactants or products, leading
to coke formation and self-poisoning through the physical blockage of the catalyst surface.
-The precursors of coke are highly condensed aromatic structures with a low hydrogen content
(H/C < 1), as well as polymerized and dehydrogenated acetylenes and unsaturated olefins.

-Molar Ratio H₂/HC

The molar ratio of hydrogen to hydrocarbons (H₂/HC) is a fundamental parameter in the
catalytic reforming process. It directly affects reactor performance, catalyst stability, and
product selectivity.
1. Importance of the H₂/HC Ratio
-Control of hydrogen partial pressure:
This ratio provides an indication of the amount of hydrogen available in the reaction mixture.
A sufficient hydrogen partial pressure promotes equilibrium in the hydrogenation–
dehydrogenation reactions and limits undesirable side reactions.
By adjusting the H₂/HC ratio, both the thermodynamic and kinetic conditions within the
reactor can be optimized.
-Prevention of coke formation:

One of the essential roles of hydrogen is to inhibit coke deposition, a solid carbonaceous
material that accumulates on the catalyst surface and reduces its activity.
An excess of hydrogen in the reaction medium hydrogenates unsaturated intermediates and
heavy aromatic compounds, thereby preventing their polymerization into coke.
Conversely, a low H₂/HC ratio accelerates catalyst fouling and decreases its lifetime.
2. Practical Implementation
In practice, the H₂/HC ratio is defined as the molar quantity of recycled hydrogen relative to
the molar quantity of hydrocarbons fed into the reactor.
This ratio is controlled by recycling part of the hydrogen produced during the reforming
reactions themselves.
An optimal ratio ensures that:
• a reducing atmosphere is maintained, favoring catalyst stability;
• coke formation is minimized;
• and the overall yield of hydrogen and aromatic products is maximized.

Catalyst regeneration in catalytic reforming

Catalyst regeneration in the catalytic reforming process is a crucial operation designed to restore
catalyst activity, maintain process efficiency, and extend catalyst lifetime.
The procedure primarily aims to remove coke and impurities, stabilize the catalyst structure,
and reactivate the active sites before the catalyst is reintroduced into service.
1. Identification of Catalyst Deactivation
Before regeneration, it is essential to determine the type and extent of catalyst deactivation.
Deactivation is mainly caused by:
Coke deposition, which blocks the pores and covers the active sites, and contaminants such as
sulfur, chlorine, or metals that poison the active phase.
A precise diagnosis allows the selection of the most appropriate regeneration method.
2. Feed Shutdown
The hydrocarbon feed is temporarily stopped before regeneration to:
prevent further contamination of the catalyst, and allow a safe transition to the oxidation
phase.
3. Coke Removal
The removal of coke is the key step in catalyst regeneration and can be carried out by
controlled oxidation or steam gasification.
a. Oxidation of Coke
A flow of air or oxygen is introduced into the reactor. The temperature is carefully controlled
between 400 and 600 °C to ensure effective combustion of the coke while avoiding damage to
the catalyst support.
Main reactions:
C + O₂ → CO₂
2C + O₂ → 2CO
The carbon deposits are converted into carbon dioxide (CO₂) and carbon monoxide (CO),
releasing heat in the process.
b. Temperature Control
The oxidation temperature must be properly regulated:
• Too high → risk of sintering (fusion and agglomeration of active metal particles).
• Too low → incomplete combustion of the coke.
c. Steam Gasification
In some cases, steam is injected into the reactor to react with coke according to:
C + H₂O → CO + H₂
This method converts coke into synthesis gas (CO + H₂) while limiting thermal stress on the
catalyst.
4. Catalyst Stabilization
After coke removal, the catalyst undergoes thermal stabilization to restore its structural and
catalytic properties.
a. Objectives of Thermal Treatment
• Restore the crystalline structure of the catalyst that may have been altered during
operation.
• Reactivate catalytic sites by redistributing and redispersing the active metal
components (e.g., Pt, Ir).
b. Operating Conditions
• Temperature: generally between 300 and 600 °C, depending on catalyst composition.
• Too high → risk of particle sintering.
• Too low → insufficient reactivation.
• Duration: optimized to ensure complete stabilization without degradation.
• Controlled atmosphere: the treatment is usually carried out under inert gas (N₂) or
reducing gas (H₂) to prevent unwanted oxidation of the active metals.
5. Controlled Cooling
After thermal stabilization, the catalyst must be cooled gradually to prevent thermal shock.
a. Importance of Controlled Cooling
• Rapid cooling can cause cracking or deformation of the support material.
• Progressive cooling helps preserve the catalyst structure and maintain the catalytic
properties restored during heat treatment.
b. Cooling Methods
• Gas-phase cooling: using inert gases (nitrogen, hydrogen) allows safe temperature
reduction without exposure to air.
• Water-cooled heat exchangers: may also be employed under strict control to avoid
condensation or contamination.
6. Chemical Reactivation
In some cases, additional chemical treatments are necessary to fully restore catalyst activity.
a. Chemical Treatments
• Acidic or basic washing: to remove remaining contaminants or deposits from the
catalyst surface.
• Reduction under reactive gases (H₂ or CO): to reduce oxidized metal species and
regenerate the active metallic phase.
b. Doping and Promoter Addition
Sometimes, promoter elements are introduced to enhance performance:
• Noble metals (Pt, Rh, Ir) increase selectivity and coke resistance.
• Support modification (e.g., alumina, silica) improves thermal stability and mechanical
strength.

7. Post-Regeneration Characterization
Before returning the catalyst to service, its performance and structure are evaluated.
 • Catalytic activity tests: conducted under reforming conditions to verify recovery of
initial performance.
• Physical and chemical analyses:
• Spectroscopic techniques (IR, UV–Vis),
• Microscopy (SEM),
• Surface area and pore structure analysis (BET).
These analyses confirm the recovery of active surface area and proper dispersion of metallic
particles.
8. Recommissioning
After complete regeneration and testing, the catalyst is reintroduced into the reforming
reactor.
Operating conditions (temperature, H₂/HC ratio, pressure, etc.) are often adjusted to:
• optimize catalyst activity and selectivity,
• minimize new coke formation,
• and extend the catalyst’s operational cycle before the next regeneration.
Regeneration of Catalysts

Etapes Objectifs

Unit shutdown and

preparation of
Unit preparation
circuits and
specific equipment

Primary
Burning of coke deposited on the catalyst during the previous cycle
combustion of coke

Secondary
Verification of complete coke combustion
combustion of coke

Metal redispersion on the catalyst surface

A step of oxychlorination that allows the removal of poisons
Oxychlorination
deposited on the catalyst, but primarily serves to redisperse the
metals and adjust the acidity of the alumina

Initial metal redispersion (restoring the dispersed metals to their

Catalyst reduction
reduced form)

Reduction of the regenerated catalyst activity to prevent rapid coking

Sulfurization and
at the beginning of the cycle (injection of the chemical DMDS –
feed injection
dimethyldisulfide – onto the catalytic beds)

Prevent the reactor temperatures from rising until the recycle gas is
Recycle gas drying
dry, in order to avoid chlorine release
 1- Primary Coke Combustion
The primary coke combustion process consists of oxidizing the carbon deposits (coke)
accumulated on the catalyst using oxygen or air. The main stages of this combustion are as
follows:
a) Controlled Air Introduction:
Air containing a low concentration of oxygen is introduced into the system. This helps limit
excessive temperature rise during the reaction.
b) Partial Oxidation of Coke:
The coke, mainly composed of carbon and hydrocarbons, is oxidized into carbon dioxide
(CO₂) and, in some cases, into carbon monoxide (CO) according to the following reactions:
C + O₂ → CO₂
2C + O₂ → 2CO
The reaction is exothermic, releasing heat.
c) Temperature Control:
Excessive primary combustion can lead to high temperatures, which may damage the catalyst.
Therefore, the control of oxygen concentration and airflow rate is essential to avoid such
negative effects.
d) Treatment of Exhaust Gases:
The gases produced (CO₂ and CO) are either treated in subsequent regeneration stages or
discharged after purification to meet environmental standards.
 Importance of Primary Combustion
 Recovery of catalytic activity:
The combustion process removes the coke deposits that block the active sites of the
catalyst, thereby restoring their accessibility to the reactants.
 Preparation for subsequent stages:
After primary combustion, a secondary combustion step may be carried out to fully
oxidize the remaining carbon monoxide (CO) and eliminate any residual coke.
Overall, primary combustion is a key stage in catalyst regeneration, essential for extending
catalyst lifetime and maintaining the efficiency of the catalytic reforming process.

2. Secondary Combustion of Coke

The secondary combustion of coke in the regeneration process of reforming catalysts is a
complementary stage that generally follows primary combustion.
This step aims to fully oxidize the remaining carbon residues and gaseous by-products
generated during the first stage, while avoiding any damage to the catalyst or process
equipment.
 Objectives of the secondary combustion:
a) Complete oxidation of carbon monoxide (CO):
During the primary combustion, part of the coke is converted into carbon monoxide
(CO).
The secondary combustion ensures that this CO is fully oxidized into carbon dioxide
(CO₂).
Chemical reaction:
2CO+O2→2CO2
b) Complete removal of residual coke:
If small amounts of coke deposits remain after the primary combustion, they are
entirely oxidized during this stage.
c) Emission control:
This step ensures that the gaseous emissions, mainly CO and CO₂, comply with
environmental regulations and safety standards.

-Operating Conditions of Secondary Combustion

 Controlled temperature:
The secondary combustion requires a moderate temperature, typically between 500
and 600 °C, in order to prevent catalyst overheating and to preserve its physical and
chemical properties.
 Oxygen enrichment:
Compared to primary combustion, the air or gas mixture used in this stage may
contain a slightly higher oxygen concentration to ensure complete oxidation of the
remaining carbonaceous species.
 Main reactions:
Oxidation of residual coke:
C+O2→CO2
[Link] of carbon monoxide:
2CO+O2→2CO2
 3. Oxychlorination
Oxychlorination is a critical step in the regeneration of catalytic reforming catalysts. It takes
place after coke combustion and aims to restore the chemical and physical properties of the
catalyst, particularly by reintroducing chlorine to re-establish the acid balance required for
optimal catalytic performance.
Objectives of Oxychlorination
1. Restoration of catalyst acidity:
Chlorine plays a crucial role in generating acidic sites on the alumina support, which are
essential for catalytic reactions in reforming processes, such as isomerization and cyclization.
2. Reactivation of metal dispersion:
Chlorine assists in redistributing the active metal particles—typically platinum and
occasionally other metals like rhenium—uniformly across the support surface, thereby
enhancing their catalytic effectiveness.
3. Maintenance of selectivity and activity:
An optimal chlorine balance maximizes the conversion of desired reactions while minimizing
undesirable side reactions, such as cracking.
Principle of Oxychlorination
Oxychlorination involves the use of a chlorinating agent (commonly hydrogen chloride, HCl,
or another chlorinated compound) combined with an oxidizing agent (such as air or pure
oxygen) to regenerate the catalyst.
Main Reactions
Chlorinated compounds interact with the catalyst to form chlorinated bonds with both the
alumina support and the active metal components:
Al2O3+HCl+O2→AlCl3+H2O
The adsorbed chlorine also promotes redispersion of the active metals according to the
following reaction:
Pt+Cl2→PtClx
-Operating Conditions
• Temperature: Typically maintained between 450 and 550 °C to favor the
oxychlorination reactions without damaging the catalyst structure.
• Chlorine concentration: Carefully controlled to prevent over-chlorination, which
may lead to catalyst loss or equipment corrosion.
• Atmosphere: A gas mixture containing HCl and oxygen is used, sometimes with
water vapor to moderate the reaction and improve distribution.
Removal of By-products
Oxychlorination produces secondary gaseous products, mainly aluminum chloride (AlCl₃) and
water vapor. These are removed or captured in downstream gas treatment units to prevent
contamination or corrosion of the system.
-Critical Points
1. Formation of by-products:
Oxychlorination generates by-products such as gaseous aluminum chloride (AlCl₃)
and water vapor. These gases must be removed or captured in dedicated treatment
units to prevent environmental impacts and corrosion issues within the process
equipment.
2. Control of temperature and chlorine concentration:
Improper management of temperature or chlorine concentration can lead to
degradation of the catalyst support or loss of active metal components, resulting in
reduced catalyst performance and shortened service life.

-After the oxychlorination step, the catalyst recovers its initial properties, including a uniform
dispersion of active metals and an optimal chlorine concentration.
-A well-controlled oxychlorination process extends the catalyst’s lifetime by preventing metal
agglomeration and excessive chlorine loss, thereby maintaining both its activity and
selectivity during subsequent reforming operations.

[Link] Reduction
Catalyst reduction is an essential step in the regeneration process of catalytic reforming
catalysts. It typically occurs after the coke combustion and oxychlorination stages. The main
objective of this step is to restore the active metals, such as platinum (Pt) or rhenium (Re), to
their metallic active state by reducing them from their oxidized forms.
 Objectives of Catalyst Reduction
1. Restoration of the active metal state:
During the oxychlorination stage, the active metals may be converted into oxides or
chlorinated complexes. The reduction process transforms these inactive species into metallic
forms, which are essential for catalyzing the key reactions involved in catalytic reforming.
2. Preparation for reforming operations:
A catalyst in its reduced metallic state exhibits the highest activity for reactions such as
dehydrogenation, isomerization, and cyclization, which are central to the reforming process.
3. Improvement of metal dispersion:
A controlled reduction ensures that the active metals remain well-dispersed on the support
surface, preventing metal agglomeration and maintaining optimal catalytic efficiency.

 Principle of catalyst reduction

The reduction process involves exposing the catalyst to a reducing atmosphere—typically
pure hydrogen or a hydrogen-rich gas mixture—at elevated temperatures.
Main Reactions
• Reduction of metal oxides:
PtO2+H2→Pt+H2O
Re2O7+7H2→2Re+7H2O
• Reduction of chlorinated complexes:
PtClx+xH2→Pt+xHCl
Operating Conditions
• Temperature: Typically maintained between 450 and 550 °C, allowing for complete
reduction without damaging the catalyst structure.
• Pressure: Usually carried out at atmospheric pressure, though moderate pressures
may be applied depending on process specifications.
• Reducing gas: Mainly pure hydrogen or a hydrogen-enriched gas mixture( ex: CH4)
• Duration: The required time depends on the catalyst bed size, temperature, and
hydrogen concentration, generally ranging from a few hours to a full day.

-After Reduction
The catalyst becomes fully reactivated: the active metals, such as platinum (Pt) and rhenium
(Re), are restored to their metallic state and are now ready to catalyze the reforming reactions.
-Maintenance of metal dispersion:
A well-controlled reduction process prevents metal migration or agglomeration on the support
surface, thereby preserving the catalytic efficiency and ensuring long-term stability of the
reforming catalyst.

5-Catalyst sulfiding (Sulfuration)

 Objectives
1. Control of catalytic activity:
Sulfiding involves introducing a small amount of sulfur onto the catalyst surface to moderate
its excessive activity, thereby reducing undesirable side reactions such as over-cracking or
coke formation.
2. Protection of active metals:
A slight sulfidation of the active metals (such as platinum or rhenium) helps stabilize their
activity by preventing overactivation of catalytic sites, which in turn extends the catalyst’s
lifetime.
 Principle:
Sulfiding is carried out by injecting a sulfur-containing compound—such as carbon disulfide
(CS₂), dimethyl sulfide (DMS), or a hydrogen sulfide (H₂S)-containing gas—into a hydrogen
stream or directly into the feedstock flow.
 Operating Conditions
Temperature: Generally maintained between 300 and 450 °C, allowing effective sulfur
adsorption without degrading the catalyst.
Sulfur content: Carefully controlled to achieve the optimal sulfur loading, typically between
0.05 and 0.5 wt% sulfur on the catalyst.
Duration: The sulfiding process typically lasts from a few hours to one day, depending on the
catalyst bed size and the method used.
-Feed injection allows verification that the catalyst is fully functional and provides adequate
conversion and selectivity.
-Final activation of metals: Active metals such as platinum reach their stable and optimal
state for reforming reactions.
-Prevention of coke formation: Feed injection stabilizes the catalyst under hydrogen-rich
conditions, minimizing the risk of coke formation.
-Sulfiding: Ensures balanced catalyst operation, providing good activity and prolonged
lifetime.
 Feed injection: Prepares the catalyst for long-term operation and ensures a gradual
startup, reducing the risk of malfunction.

6-Drying of the Recycle Gas

The drying of the recycle gas is an important step in the regeneration of the catalytic reforming
catalyst, especially after stages such as reduction or sulfiding. This operation ensures that the
recycled hydrogen used in the process is free of moisture, which is essential to protect the
catalyst and optimize performance.
 Objectives of Recycle Gas Drying:
• Removal of residual moisture:
During previous steps (such as combustion or oxychlorination), water may be
produced or introduced into the system. Drying removes this moisture to prevent
undesirable reactions with the catalyst.
• Prevention of catalyst degradation:
Moisture can react with chlorinated compounds remaining on the catalyst (after
oxychlorination) and cause chlorine loss, which would decrease the catalyst’s activity
and selectivity.
• Ensuring efficient operation:
A dry gas promotes better conversion during catalytic reforming and minimizes
operational issues such as corrosion or coke formation.
 Chapter II :Catalytic Cracking

2.1. Thermal Cracking: The primary source of the required energy is heat. Since the reactions
involved are endothermic, they are favored by high temperatures and low pressure.

2.2. Catalytic Cracking: This process allows the production of simpler molecules by
fragmenting complex hydrocarbons (converting heavy petroleum products into lighter ones),
thereby improving product quality, increasing the yield of more valuable light products, and
reducing the quantity of residues. From a thermodynamic standpoint, cracking reactions are
favored at high temperatures (approximately 450–550 °C) and low pressure in the presence of
a catalyst. Large hydrocarbon molecules are broken down to produce smaller molecules with a
high octane number. The process proceeds via an acidic mechanism; thus, catalysts used in
refinery cracking units are porous solid materials (zeolites, aluminum hydrosilicates, treated
bentonite clay, and silicoaluminates) presented in the form of powders, beads, pellets, or shaped
granules called extrudates.

2.3. Reaction Mechanism:

The carbonium ion: Catalytic cracking gasoline, particularly its lighter fractions, contains a
high proportion of isomerized structures, both olefinic and paraffinic, while its heavier fractions
are strongly aromatic.

Butanes, which are produced in large quantities, are also extensively isomerized, and the olefin
content of the C3–C4 cut is significant.

 In thermal cracking, the electron pair that binds the nuclei of two carbon atoms
separates such that one electron remains on each nucleus, leading to the formation of
free radicals:

In catalytic cracking, the electron pair remains on the same carbon nucleus while the other
electron becomes positively charged, leading to the formation of a positively charged species,
known as a carbonium ion.
Formation of the Carbonium Ion
The carbonium ion is a fleeting intermediate resulting from the addition of a proton (H⁺) from
the catalyst to an olefin.

This addition is accompanied by the release of heat.

The ion can, in turn, add to another olefin to form a longer carbonium ion.

This alkylation or polymerization is accompanied by the release of heat. In cracking, the exact
opposite reaction occurs:

Catalytic Cracking Processes

The catalytic cracking process has three basic functions:

 Reaction

 Catalyst regeneration and reactivation through coke combustion

 Fractionation: the products obtained from cracking are separated into various fractions

Coking: Coking is an intensified thermal cracking process that produces straight-run gasoline
(coking naphtha) and various medium distillates, which are then sent to catalytic cracking
units.
Deasphalting: This operation consists of removing asphaltenes. It is carried out in an extraction
column using propane. The process yields a viscous oil rich in aromatic compounds, which
confers low oxidation resistance. Natural asphalts (or natural bitumen) are extra-heavy crudes
with a very viscous to solid consistency.

Viscoréduction (Viscosity Reduction): Viscoréduction is a form of moderate thermal cracking

of heavy mixtures that reduces the pour point of waxy residues and significantly decreases the
viscosity of the product without altering its boiling range. The atmospheric distillation residue
is subjected to moderate cracking at atmospheric pressure in a heater. The temperature is rapidly
lowered using cold diesel to prevent excessive cracking, and the mixture is then expanded in a
distillation tower. The residual tar produced during thermal cracking, which accumulates at the
bottom of the fractionation column, is subjected to vacuum expansion in a rectification column,
and the distillate is recycled.

Types of Catalytic Cracking Processes:

There are three types of catalytic cracking processes:

1. Fluid Catalytic Cracking (FCC) – catalytic cracking on a fluidized bed

2. Moving Bed Catalytic Cracking – catalytic cracking on a moving bed

3. Moving Bed Catalytic Cracking according to the TCC process (Thermofor Catalytic
Cracking)
 Chapter III : Conversion Processes by Combination

[Link]
Polymerization is a process that allows the combination of at least two unsaturated organic
molecules (olefins) into a single, heavier molecule in which the elements of the original
molecules are present in the same proportions. It converts gaseous olefins, such as ethylene,
propylene, and butylene, obtained from thermal cracking and fluidized bed cracking units, into
more complex and heavier molecules with a higher octane number, such as naphtha. A
phosphorus-based catalyst, typically a solid catalyst or liquid phosphoric acid, is used, and an
exothermic polymerization reaction occurs.

[Link]
Alkylation combines olefin molecules obtained from catalytic cracking with isoparaffin
molecules, thereby increasing both the volume and the octane number of the base gasoline. The
olefins react with the isoparaffins in the presence of a highly active catalyst, typically sulfuric
acid or hydrofluoric acid (or aluminum chloride), to produce a long-chain branched paraffinic
molecule.

[Link]
Isomerization allows the conversion of n-butane, n-pentane, and n-hexane into their respective
isoparaffins. Some of the constituents of the linear paraffins in light naphtha obtained from
straight-run distillation have a low octane number. These constituents can be converted into
branched isomers with a higher octane number by rearranging interatomic bonds without
changing the number or type of atoms.

Isomerization is similar to catalytic reforming, as it also involves the rearrangement of

hydrocarbon molecules; however, unlike catalytic reforming, isomerization only converts linear
paraffins into isoparaffins. The catalyst used for isomerization is different from that employed
in catalytic reforming.

 Isomerization is an operation that transforms a linear paraffin into an isomerized

paraffin to increase its octane number. The feedstock for an isomerization unit is light
naphtha (C5–C6).
There are primarily two fundamental reactions:

 Benzene hydrogenation

 Isomerization

The first reaction is highly exothermic. To monitor the isomerization temperature, benzene
hydrogenation occurs in the first reactor. The second reaction is the isomerization reaction
itself, which takes place in both reactors.

 Benzene Hydrogenation:
Benzene reacts with hydrogen to form cyclohexane.

Benzene hydrogenation is an exothermic reaction (16,800 kcal per kmol of hydrogen

consumed).

 Isomerization
Isomerization is the conversion or rearrangement of a compound’s structure into a more
branched structure with a higher octane number.
The three naphthenes generally present in an isomerization feed are cyclopentane (CP),
methylcyclopentane (MCP), and cyclohexane (CH). These naphthenic rings are opened and
hydrogenated to form paraffins. The ring-opening reactions increase with rising temperature.

Under low-severity reactor conditions, very little hydrocracking of C5/C6 occurs in the
isomerization reactors. C7 paraffins, however, are easily hydrocracked to produce C3 and C4
components. Most hydrocracking occurs in the first reactor, which generally operates at a
higher temperature. Hydrocracking reactions consume hydrogen, and consequently, it is
recommended to limit the C7+ content of the isomerization feed.

The isomerization catalyst is platinum-based on chlorided alumina for the isomerization of

C5–C6 cuts.

Catalyst Contaminants

 Sulfur
The presence of sulfur in the feed or hydrogen make-up will immediately decrease catalyst
activity. Sulfur reacts with platinum to form platinum sulfide, which reduces the metallic
function of the catalyst and affects the hydrogen transfer mechanism.
 Water / Oxygenates

Oxygenated components chemically react with the active chloride on the catalyst. Water,
once it reacts with the catalyst, is chemically bound as hydroxyl groups on the alumina, and
the chloride is removed as HCl.
 Nitrogen Components

This includes organic nitrogen or ammonia. Nitrogen components react to form ammonia,
which in turn reacts with the chloride in the catalyst or with HCl to form ammonium
chloride salt. This leads to permanent catalyst deactivation by coating the active sites of the
catalyst.

 Fluorine Components

These are also permanent catalyst poisons, caused by the binding of fluoride to the active
sites of the catalyst, which affects the catalyst acidity.

Process Variables
There are five primary process variables that have a direct effect on the performance of an
isomerization reactor:

 Reactor temperature

 Space velocity

 Hydrogen-to-hydrocarbon ratio

 Feed composition

 Reactor outlet pressure

 Chloride injection