Catalytic Reforming

PGS.TS. Trương Hữu Trì

CATALYSTS POISONS
 Catalyst Poisons
• The most common type of catalyst poisoning is caused by any
impurity that is either present in the gas stream or formed by
some process during reactions.
• The poison becomes adsorbed on the active sites of the catalyst
causing either a temporary or permanent decrease in the all over
activity.
 Catalyst Poisons
 Temporary poisons
• Temporary poisons which can be removed and the proper
activity and selectivity of catalyst is restored.
• The most common temporary poisons (inhibitors) are:
 Sulphur
 Organic nitrogen
 Water
 Oxygenated organics
 Halogens
 Catalyst Poisons
 Temporary poisons
• Sulfur present as impurities in the naphtha feed stock in
concentrations of organic sulfide of up to 1500 ppm;
• Sulfur is known to adsorb strongly at very low gas phase
concentration and can remain as a very stable adsorbed
species under different reaction condition.
• The sulfur limits in each catalyst:
 Monometallic Pt/Al2O3 : < 20 ppm;
 Bimetallic catalyst Pt-Re/Al2O3 : < 1 ppm;
 Catalysts containing higher Re/Pt ratio are more sensitive to
sulfur compound, maximum sulfur of 0.5 ppm is allowed
 Catalyst Poisons
 Temporary poisons
Effect of sulfur on Reforming of naphtha feed at constant catalyst life
 Catalyst Poisons
Temporary poisons
• Nitrogen compounds are generally present in the form organic
compounds that decompose into ammonia at reforming conditions;

 Poisoning due to nitrogen

compounds are known to
inhibit principally the
acid function of the
catalyst;
 Catalyst Poisons
 Permanent poisons
• 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
 Catalyst Poisons

• Metal contamination generally causes a decrease in the

dehydrogenation and dehydrocyclization functions;
• Platinum metal can be activated by metallic ions such a mercury,
arsenic, lead, bismuth, copper and iron;
• Small amounts of iron and copper can accelerate the deactivation in
the dehydrocyclization reaction;
• Effect of arsenic on Pt/Al2O3: an increase in arsenic concentration
on catalyst to 0.5 wt% decreases dehydrogenation activity.
 Catalyst Poisons
 Permanent poisons

Temporary
Semipermanent

Permanent

Difference between inhibitors and permanent poisons

CATALYSTS STABILITY
 Catalyst 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
• Degree of poisoning of deposited coke
• Relative coking rate
CATALYSTS REGENERATIONS
 Catalysts regenerations
 Objectif: Recover initial catalyst activity

 Coke removal → 2 Burning zones

 Metal redistribution & chloride adjustment

Oxychlorination

 Catalyst drying → Calcination

Each zone independently optimized

Catalysts regenerations
Catalysts regenerations

Schematic diagram of platinum

redispersion by oxychlorination
Catalysts regenerations
Catalysts regenerations
 OUTLINE

1 Introduction of upgrading process

2 Fundamentals of catalytic reforming

3 Catalyst in catalytic reforming

4 Operating variables

5 Process technology
19
 Operating Variables
 Process variables that may be adjusted by design or during
operation include:
 Reactor temperature
 Space velocity
 Pressure
 Hydrogen/hydrocarbon ratio
 Feedstock characteristics

 The relationships of the variables generally apply to both fixed-

bed reforming and continuous reforming
 Operating 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)
 Operating Variables
 Reactor temperature

 Primary control of changing conditions or qualities in reactor;

 High temp increase octane rating;

 High temp reduce catalyst stability but may be increased for

declining catalyst activity. The high temperatures, above
560°C, may cause thermal reactions which will decrease
reformate and hydrogen yield and increase coke formation.
 Operating Variables
 Reactor 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)

Where Ti1, Ti2, … are inlet temperature of reactors

(wt of catalyst R1) are weight of catalyst in reactors
 Operating Variables
 Reactor 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
 Operating Variables
 Reactor temperature
 With time, temp is raired gradually to offset the effect of catalyst deactivation
by coking.
 Operating Variables
 Reactor temperature
 The temp TSOR required to achieve a specified RON is directly related to the
RON under certain conditions as indicated in figure below.

Variation in
octane number
versus TSOR
 Operating Variables
 Space velocity
 Weight hourly space velocity:

 Liquid hourly space velocity:

 Linked to residence time of feed in the reactor and affects

the kinetics of the Reforming reactions
 Operating Variables
 Space velocity
 Space velocity has an effect on product quality;
 The higher the space velocity (lower residence time) the lower the product
RONC or the less the amount of reaction;
 At very low LHSV,
thermal reactions can
Influence of space velocity on
reformale octane number
occur to a sufficient
degree to decrease
reformate and hydrogen
yields.
 Operating Variables
 Reactor pressure
 Pressure effects the reformer yield & catalyst stability;
 Low pressure increases yield & octane;

 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)
 Operating Variables
 Reactor 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
 Operating Variables
 Reactor pressure
 Operating Variables

Influence of P and the feed on C5+ yield

 Operating Variables
 H2/HC ratio

 Moles of recycle hydrogen / mole of naphtha charge;

 Increase H2/HC ratio will decrease the catalyst coking rate with
little effect on the product quality or yields.

 An increase in H2/HC ratio will move the naphtha through the

reactor at a faster rate and supply a greater heat sink for the
endothermic heat of reaction.
 Operating Variables
 H2/HC ratio
 Operating Variables
 Influence of feeds
 Feeds are defined either by the overall characteristics: KUOP, N+2A,
IBP, EP or by the hydrocarbon family and number of carbon atoms.
 Operating Variables
 Influence of feed: Feed quality chemical composition
Characterization of the feedstocs by: 0.85N + 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. T The endothermic reaction heat is he
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
capacitycapacity
 Impurities
• Temporary or permanent reduction of catalyst activity by poisons
contained in the feed
 Operating Variables
 Influence of feed: 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 180oC are generally not recommended

 Operating Variables
Summary on cause and effect table:
 Operating Variables
Summary on cause and effect table:
 Operating Variables
Summary on cause and effect table:
 OUTLINE

1 Introduction of upgrading process

2 Fundamentals of catalytic reforming

3 Catalyst in catalytic reforming

4 Operating variables

5 Process technology
41
 Process Technology
Current catalytic reforming processes are commonly classified into
three types based on regeneration systems work of the catalyst.
These includes:

 Semi-regenerative catalytic
reformer process (SR)
Fixed Bed Reactor
 Cyclic regenerative catalytic
reformer process (CR)

 Continuous catalytic regeneration

reformer process (CCR)

Moving Bed Reactor

 Process Technology

 SR is the oldest reforming process that is used for the production

of gasoline and rich aromatic compounds.
 It usually has three or four reactors in series with a fixed-bed
catalyst system.
 A semi-regenerative process uses low platinum and regeneration
is required only once a year.
 Process Technology
 Semi-regenerative catalytic reformer process
 Process Technology
 Semi-regenerative catalytic reformer process: Platforming
 Process Technology
 Semi-regenerative catalytic reformer process
 Process Technology
 Semi-regenerative catalytic reformer process: Platforming

 The semi-regenerative system provides a total duration of catalyst

utilization of about 7-10 years and even longer;
 When the reactors reach end of cycle levels, the reformer is shutdown
to regenerate the catalyst in situ;
 Ancillary units are designed to allow optimum use of catalysts and to
offset some of their drawbacks: a feed purification section;
compressing and recycling part of the hydrogen produced during the
reaction; in a stabilization section.
 Process Technology
 Cyclic regenerative catalytic reformer process
 Process Technology
 Cyclic regenerative catalytic reformer process

 Regenerative (Cyclic), which involves the regeneration of a part of the

catalyst after its deactivation, during switching the operation to a
swing reactor, with no shutdown of the unit;
 With a complex valve system, three reactor can be running while the
fourth is being regenerated.
 The catalyst is regenerated without stopping the unit allows for a lower
severity than that in the semi-regenerative system.
 The regeneration of the catalyst is carried out at short time intervals,
on average 5-15 days.
 Process Technology
 Cyclic regenerative catalytic reformer process: Hydroforming

 The hydroforming process made use of molybdena-alumina (MoO2-

Al2O3) catalyst pellets arranged in fixed beds; hence the process is
known as fixed-bed hydroforming;
 The hydroformer had four reaction vessels or catalyst cases, two of
which were regenerated; the other two were on the process cycle;
 Naphtha feed was preheated to 400°C to 540°C and passed in series
through the two catalyst cases under a pressure of 150 to 300 psi.
 Process Technology
 Cyclic regenerative catalytic reformer process: Powerforming
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Exxon
 Process Technology
 Cyclic regenerative catalytic reformer process: Powerforming
 Reforming takes place in several (usually four or five) reactors and
regeneration is carried out in the last (swing) reactor;

 The plant need not be shutdown to regenerate the catalyst;

 The cyclic process assures a continuous supply of hydrogen gas for

hydrotreatment operations and tends to produce a greater yield of
higher octane reformate.
 Process Technology
 Moving-Bed: Reactor Configuration

 UOP put a continuous regeneration system on the market, where three

or four reactors are located one on top of the other;
 The catalyst moves downward by gravity from R1, to R2 then R3,
loaded with coke, by a lift to the top of the regenerator.
 It goes through the regenerator by gravity then sent back to the top of
R1.
 The rest of the unit flow scheme is very close to the fixed bed process.
 Process Technology
 Moving-Bed: Advantages
 Reformates are produced with a very high octane number even from
difficult feeds and without any run duration problems;
 Units are operational all year round, regularly producing the hydrogen
that modern refineries constantly need;
 Catalysts are less stable over time but more selective, making it
possible to improve yields;
 Recycle rates are lower, thereby improving yields and reducing
operating costs;
 Operating pressures are significantly lower and this is highly
favorable for the reformates and the hydrogen yields.
 Process Technology
 Moving-Bed: IFP "Octanizing" Process
 Process Technology
 Moving-Bed: IFP "Octanizing" Process
 Process Technology
 Moving-Bed: UOP "CCR" Platforming Process

Continnous regeneration
reformer (UOP: Platforming).
 Process Technology
 Moving-Bed: UOP "CCR" Platforming Process
 Process Technology
 Moving-Bed: UOP "CCR" Platforming Process at BSR
 Process Technology
 Moving-Bed: UOP "CCR" Platforming Process
 The Platforming process has since become a standard feature in
refineries worldwide;
 In the CCR Platforming unit, partially coked catalyst in the reactors is
continuously replaced with catalyst that has been freshly regenerated
in an external regenerator (CCR section) to maintain a low average
coke for the reactor catalyst;
 The CCR Platforming unit uses a UOP-patented reactor stack. The
reactors are stacked one on top of another to achieve a compact unit
that minimizes plot area requirements.
 Process Technology
 Moving-Bed: UOP "CCR" Platforming Process
 The catalyst flows gently by gravity downward from reactor to
reactor, and this flow simplifies catalyst transfer and minimizes
attrition;
 In the CCR process, catalyst is lifted only twice during each cycle:
from the bottom of the reactor stack to the top of the regenerator and
then from the bottom of the regenerator back to the top of the
reactor stack.
 Process Technology
 CCR Platforming versus Fixed-bed Platforming
 Process Technology
 Advantages of CCR Continuous Reforming Technology

 High utilization of feed due to low operating pressure

 On stream factor of more than 95%
 Flexibility to process a wide variety of feedstock
 Only two catalyst lifts for minimal catalyst attrition
 Stacked reactors for economical design
 Optimized heat and compression integration for every unit
 Liquid recovery optimized on every unit
 Process Technology
 Disadvantages of CCR Continuous Reforming Technology

CCR process shows disadvantages of complicated process

flow and more investment as an additional continuous catalyst
regeneration system is provided.
Note: However, it can contribute to high octane product, high
product yield, long unit operation cycle and flexible operation.
Process Technology
 Comparison of
CCR process
and Semi-
Regeneration
Reforming
Process
 Process Technology
 Comparison of CCR process and Semi-Regeneration Reforming Process

Basis: Same Feedstock processed

 Process Technology
 Some of the main features, Advantages and Disadvantages of each type of
Catalytic Reforming Processes
 Process Technology
 Reactors
• Two types of the flow pattern
 Process Technology
 Typical Radial Reactors
Process Technology
 Typical Radial
Reactors
Process Technology
 Typical Axial Fixed – Bed Reactors
 Process Licensors

Various commercial
catalytic reforming
processes