Catalytic Reforming

Refiners throughout the world utilize catalytic reforming to produce high-octane

reformate for gasoline blending and high value aromatics (benzene, toluene and xylene,
BTX) for petrochemical use. Reforming is also a major source of refinery-based
hydrogen. Reforming operations continue to be challenged in the context of lowering
gasoline pool aromatic/ benzene content; however, the catalytic reforming unit is still a
mainstay of refinery operations. The recent upward trend in hydrotreatment needs has
put even more emphasis on reformer hydrogen production.

Process chemistry
The distribution of the hydrocarbon types (paraffins, naphthenes and aromatics) will
determine how easily various naphthas can be reformed. Aromatic compounds pass
through the reforming unit relatively unchanged; naphthenes react rapidly and efficiently
to aromatics, while paraffins react slowly and with less selectivity. A generalized reaction
scheme that identifies these key reactions, as well as the reaction pathways that are
required to achieve high product yields, is depicted in Fig. 2. Two key catalyst functions
are served by acid and metal sites. Three major reactions shown in Fig. 3,
dehydrocyclization, isomerization, and dehydrogenation, occur in a reforming unit to
produce the desired products. Reactions such as hydrocracking and dealkylation (Fig.
4) are undesirable.
Feedstock

The standard feed to a catalytic reforming unit (CRU) is hydrotreated straight-run

naphtha (SRN), typically containing C 6 through C11 paraffins, naphthenes and aromatics.
Naphtha from different sources varies greatly in its ease of reforming. Most naphthenes
react rapidly and efficiently to form aromatics. This is the basic reaction of reforming.
Paraffins are the most difficult compounds to convert. A rich naphtha (lower paraffin,
higher naphthene content) makes the operation much easier and more efficient. The
types of naphtha used as feed to the CRU can impact the operation of the unit, activity
of the catalyst and product properties. When catalytic reforming is used mainly for BTX
production, a C6-C8 cut (initial and final boiling points IBP-FBP 60140C), rich in C 6, is
usually employed. For production of a high-octane gasoline pool component, a C7-C9
cut (IBP-FBP 90160C) is the preferred choice. Reformate benzene content can be
reduced by minimizing the amount of benzene and benzene precursors (cyclohexane
and methylcyclopentane) in the reformer feed via prefractionation. Alternatively, the
benzene can be reduced by post fractionation of the reformate and further processing of
the light reformate. In a refinery where maximization of middle distillate production is a
priority, the heavier portion of the naphtha that is traditionally routed to a catalytic
reformer unit may instead be sent to the kerosene or diesel pool, within flash point
specification limits. In most cases, a lighter CRU feed will result in an increased cycle
length for a semiregenerative (SR) unit due to decreased coke make.

Non-straight-run naphthas (for instance, fluid catalytic cracking (FCC) naphtha or

visbreaker/coker naphtha) can also be processed in a CRU, but only after severe
hydrotreatment involving (di)-olefin saturation, in addition to the basic naphtha
hydrotreater functionality of removing heterogeneous atoms (sulphur and nitrogen).
Their higher endpoint and/or higher paraffin content results in a higher coke laydown.
Cyclic and continuous catalyst regeneration (CCR) reformers are generally able to
process FCC naphtha with a higher feed endpoint as long as regenerator capacity
exists to burn the additional coke that is produced. The reprocessing of FCC naphtha is
typically restricted to the lower octane middle cut. If desulphurization only is required,
processing the FCC naphtha in a selective hydrotreating unit is the more straightforward
solution.

CATALYST:
The catalyst used for reforming is a bifunctional catalyst composed of platinum metal on
chlorinated alumina. Platinum is the centre for the dehydrogenation reaction.
Chlorinated alumina is an acidic site to promote structure changes cyclization of
paraffins and isomerization of the naphthenes

With a platinum catalyst, the process is sometimes described as "platforming". The

process has undergone continuous development with respect to catalyst performance
and process design. Bimetallic catalyst with platinum as one of the catalyst component,
the other being rhenium, ruthenium or tin have been introduced. These catalysts are
highly stable thus allowing for high conversion severities. Bimetallic catalysts use less
platinum then the earlier version thus improving the process economics Market forces
still exert demand on better reforming catalyst that would increase the yield of octane,
reduce the operating pressure, minimize the hydrogen to hydrocarbon ratio, minimize
precious metal cost and have ability to process paraffinic feedstock.
PLATINUM ON ALUMINA:

The amount of platinum dispersed on alumina is 0.3 to 0.6 wt: %. Chlorine is also
present in the amount 0.3 to 1.0%. These catalysts are prepared by impregnation of
alumina with chloroplatinic acid followed by calcinations in air between 825 to 875 K.
Surface area of the alumina used is150-300 m 2/g. The pressure drop and diffusion
limitations determine the shape of the reforming catalyst and the preferred catalyst
shapes are usually pellets or extrudates. Dispersion of the metal on alumina support is
a critical parameter for reforming as for any catalytic process, and is defined as the ratio
of the amount of exposed metal on the surface to the total amount of the metal in the
catalyst.

Acid properties of alumina: Alumina known to be amphoteric, has a lot of

hydroxyl group on its surface which are the prime source for Bronsted (protonic) acidity
and responsible for hydrocarbon rearrangement reactions. The presence of chlorine in
reforming catalysts is thought to impart acidity in alumina by interacting with the surface
hydroxyl groups.

PLATINUM RHENIUM CATALYSTS:

Rhenium (Re) is added to operate at lower pressures .These alumina supported

bimetallic catalysts generally contain an amount of rhenium comparable to the amount
of platinum. These catalysts are prepared differently from other bimetallic catalysts.
Dirhenium decacarbonyl, Re2(CO)10 are used to impregnate platinum supported on
alumina. In these catalyst, rhenium exists in the reduced form and is extremely sensitive
to poisoning by sulfur and less sensitive to coke deactivation compared to platinum.

PLATINUM IRIDIUM CATALYSTS:

Iridium (Ir) is added to boost activity. Iridium bimetallic clusters are prepared by
impregnating the alumina support with an aqueous solution of chloroplatinic and
chloroiodic acids. After impregnated support is dried and calcined at mild condition, it is
exposed to flowing hydrogen to reduce platinum and iridium. Total metal content in
these catalysts is 0.5 to 1 %.

PLATINUM TIN CATALYSTS:

Tin (Sn) is added to improve yield at low pressures. These catalysts are introduced in
catalytic reforming units by UOP with their Continuous Catalytic Reforming (CCR)
Process. The combine platinum and tin content of these catalysts is less then 0.8% wt.
%. These catalysts are prepared using chlorided precursors and are reduced above
673K. The Pt-Ni catalysts are focus of intense research because of two issues: the
oxidation number of Sn after exposure of the catalyst to hydrogen and the extent to
which bimetallic entities of Pt and Sn are present

DEACTIVATION AND REGENERATION OF CATALYSTS:

The heart of the naphtha reforming process is the catalyst and most of the process
improvements have related to catalyst life and stability.

Deactivation is very important in commercial operation because it influences the choice

of operational conditions and fixes the cycle length between regeneration and the total
life of the catalyst. Catalytic reforming has one of the more complicated deactivation
phenomena because catalyst presents nearly all the known deactivation causes.

Impurities that might cause deactivation or poisoning of the catalyst include: coke,
sulphur, nitrogen, metals and water. The reformer should be operated at high
temperature and low pressure to minimize coke deposition.

COKING: Coke can also deposit during hydrocracking resulting in the deactivation of
the catalyst. Coke formation is favoured at low partial pressures of hydrogen.
Hydrocracking is controlled by operating the reaction at low pressure between 525
atm, not too low for coke deposition and not too high in order to avoid cracking and loss
of reformate yield.

Coke deposit depends on catalyst composition, operational conditions and feed

composition. Coke formation is the most rapid cause of deactivation in naphtha
reforming. Coke deposition occurs throughout commercial operation on both acid and
metal sites with the rate of deposition being higher in the beginning. It is believed that
initial rapid coke deposition occurs mainly on metal sites. At longer time operations, the
acid site is more deactivated by the slow coke deposition.

Commercial naphtha reforming catalysts typically control the main reactions namely
Isomerization and dehydrogenation of C 6-C9 paraffins through the acid functioning.
However if the metallic function is less active or the working pressure is very low, the
metal may become the controlling function of the main reforming reactions.

1. First mechanism suggests that a series of fragmentation and successive

dehydrogenation reaction forming carbon atoms which may combine to form
graphite and toxic coke deposits.
 2. The second mechanism suggests that the route of coke deposition is based on
polymerization reactions with the formation of different carbonaceous deposits on
the metal surface.
3. Coke formation on acid sites is assumed to arise from polymerization of
dehydrogenated intermediates generated by metallic function.

Reforming catalysts are also deactivated because of poisoning by sulfur and nitrogen
compounds, sintering (decrease of metallic area), decrease of chloride concentration,
and heavy metal deposition.

REGENERATION: Catalyst regeneration include several steps such as

Elimination of coke by controlled burning

Oxychlorination to revive the metal and acid functionalities
Reduction with hydrogen and
Activation by sulphating

PROCESS CLASSIFICATION: Catalytic reforming processes are classified, based on

the mode and frequency of catalyst regeneration. There are three types

1. Semi regenerative
2. Cyclic ( fully regenerative )
3. Continuous Regenerative ( moving bed)

Semi-regenerative reforming
In a typical semi-regenerative reforming unit, treated naphtha feed is combined with
recycled hydrogen gas and heat exchanged against reactor effluent. The combined feed
is then raised to the reactor section. Down-flow or radial-flow reactors are arranged in a
conventional side-by side pattern. The catalyst deactivates over time at reaction
conditions. Typical cycle lengths range from six to twenty-four months. Generally, in-situ
catalyst regeneration for rejuvenation of the catalyst is conducted. After the catalyst has
deactivated to the point where the desired product can no longer be achieved, the unit
is taken off-line, the reactors are purged of hydrocarbons and the catalyst is
regenerated. Regeneration employs a low concentration oxygen environment that burns
the coke from the catalyst. The unit can then be placed back on stream with near new
catalyst performance. Over the course of many years and regeneration cycles, the
catalyst will loose the ability to be rejuvenated to nearly new performance and it is
replaced.
The advent of bi and multi metallic catalysts allows the operation of semi regenerative
reformer at 14-17 atm. For the same cycle lengths compared to higher pressure of 30
atm. Using Pt. Semi regenerative reformers are built with usually 3 or 4 catalyst beds in
series. The product RON achievable through this is usually 85-100 depending on
optimized feedstock quality, gasoline qualities and quantities, and operating conditions
required to achieve a specified cycle length.
Cyclic regenerative reforming

Cyclic regenerative reforming is an extension of the semi-regenerative paradigm. In

cyclic reforming, fixed-bed reactors swing in and out of reforming service and are
regenerated individually. This allows for nearly continuous operation of the reforming
unit. Typically, there are five or six reactors and large valves permit the removal of any
reactor from the process for regeneration. Cyclic operation allows higher severity
(hence, higher RON) than semi-regenerative reforming. The regeneration is often
suboptimal. Catalyst regeneration takes place at longer intervals as compared to the
semi regenerative processes. The cyclic reformer operates at a low pressure, wide
range of boiling feed and low hydrogen to hydrocarbon ratio.

The cyclic process produces reformate of RON 100-104 but also leads to extensive
coking due to low pressure.

Continuous reforming

Continuous catalyst regeneration is a complete departure from the semi-regenerative

paradigm, in that operation and performance are constant and smooth. Radial-flow
reactors are arranged in a vertical stack for CCR Platforming units. Catalyst flows
vertically by gravity down the stack, while the charge flows radially across the anular
catalyst beds. Over time, coke builds up on the Platforming catalyst at reaction
conditions. Partially deactivated catalyst is continually withdrawn from the bottom of the
reactor stack and transferred to the CCR regenerator. The catalyst flows down through
the regenerator where the accumulated carbon is burned off and the moisture and
chloride levels are adjusted. Regenerated catalyst is lifted with hydrogen to the top of
the reactor stack. Since the reactor and regenerator sections are separate, each can
operate at its own optimum conditions. In addition, the regenerator section can be
temporarily shut down for maintenance without affecting the operation of the reactor and
the product recovery sections. Regeneration sections are tailored to provide fresh
condition catalyst to the reactors. Each step is optimized.

Typical advantages of continuous reforming technology include:

a) High utilization of feed due to low operating pressure;

b) On stream factor of more than 95%;
c) Flexibility to process a wide variety of feedstock;
d) Only two catalyst lifts for minimal catalyst attrition;
e) Stacked reactors for economical design;
f) Optimized heat and compression integration for every unit; and
g) Liquid recovery optimized on every unit.

One of the key factors in maintaining catalyst performance (particularly, constant

reformate and hydrogen yields) throughout catalyst life is the ability of the CCR
regenerator to completely regenerate the catalyst.
Reactor design

There are three types of reactors predominantly in use in the reforming process. These
are spherical, down flow and radial. Reactor systems are selected depending on
reforming unit configuration. Initially, axial downflow reactor systems were used as they
were cheaper but the huge pressure drops created by them led to the usage of radial
downflow reactors in fixed bed systems. Presently, many reforming units uses a
combination of both types of reactors. At lower pressure, the pressure drop through the
reactor becomes an important consideration; therefore, more modern designs of
reforming units employ reactors that are radial flow in design and combine good flow
distribution with low pressure drop.
The combined feed is directed from the reactor inlet nozzle into so-called scallops,
which are long, vertical channels positioned along the entire circumference of the
reactor. The scallops have holes or, more commonly these days, profile wire screens
along the entire length, through which gas passes radially into the annular catalyst bed
and inwards to a centre pipe that collects the reactor products and directs them to the
reactor outlet. Low flow should be avoided, as it will result in accelerated coke lay down.

A radial reactor is a cylindrical vessel with especially designed internals. Figure 1 shows
the main internals in a radial flow fixed bed reactor (RFBR). The main internals that
provide the radial flow pattern inside the reactor are the inlet distributing header in the
form of perforated channels positioned around the circumference of the vessel, and the
axial outlet collecting header in the form of a perforated cylinder which is called the
center pipe. The catalyst is charged to the annular space between the inlet distributor
and the center pipe. The top of the catalyst bed is covered with a cover plate. There are
two types of inlet distributors. One consists of a wire screen while the other consists of a
series of scallops (Little, 1985), where each scallop is a small diameter perforated half
cylinder.

Reactor metallurgy

Reactor vessels in a SR CRU service are standalone items and can be either hot or
cold shell, depending on design preference. In cold-shell designs, an internal refractory
lining protects the vessel wall from exposure to the process temperature. In CCR
service, the reactors are invariably of the hot-shell design and can be either individually
positioned or stacked to form a compartmented single vessel.8 In a SR CRU, a cold
wall (carbon steel with refractory lining) with an inner stainless steel liner is the norm.
However, hot shell design necessitates the use of 1.25Cr-0.5Mo, or in some cases
2.25Cr-1Mo, with stainless steel internals suitable for service above 538C (1000F) to
meet the requirements for both high-temperature strength and resistance to hydrogen
attack.

CATALYTIC REFORMING PROCESSES

FEED PRETREATMENT:

The prime objective of feedstock pretreatment is removal of permanent catalyst poisons

such as arsenic, lead and copper and to reduce temporary catalyst poisons such as
sulfur, oxygen and nitrogen to lower levels.

The limits for permanent poisons and temporary poisons are

Sulfur < 10 ppm or 5 ppm on high severity

Nitrogen < 1 ppm
H2O < 4 ppm
Pb + As + Cu < 20 ppb

Semi-regenerative Fixed Bed Process: (SRR).

 Fixed bed of catalyst is used. The reaction section of a reformer unit consists of multi-
bed reactors in series with pre and re-heaters between the reactors. Desired product
RON requires at least three or four reactors. Three reactors are installed in series. All of
the catalyst is regenerated in situ during routine catalyst regeneration shutdowns (6 to
24 months) by burning off the carbon formed on the catalyst surface.

In first reactor, reactions such as dehydrogenation of paraffins and naphthenes are very
rapid and highly endothermic. The reaction temperature in first reactor decreases
rapidly due to dehydrogenation of cycloalkanes to aromatics which consumes heat. The
effluent from the first reactor is then heated and fed to the second reactor where it
undergoes dehydroisomerization of cyclopantanes at a slower rate than in the first
reactor.

In second reactor, Reactions that are considered rapid, such as paraffin isomerization
and naphthens dehydroisomerization, give moderate temperature decline.

In third reactor, slow reactions such as dehydrocyclization and hydrocracking which is

xothermic leading to slight temperature changes.

Reactor 1 Reactor 2 Reactor 3

Inlet temp K 775 775 775
Exit temperature 706 844 769
K
Temp. Drop 69 31 6
Octane Number 65.5 79.5 90
Octane Number. 27 14 10.5
increase
Principal reactions Dehydrogenation, Dehydrogenation, Hydrocracking,
dehydroisomerizatio dehydroisomerization dehydrocyclization
n , hydro cracking,
dehydrocyclization
Space velocity /h 5.5 2.4 1.7
Percent of total 15 35 50
catalysts charged

The first reactor is the smallest in size followed by the second while the third and fourth
are very large reactors reflecting the time taken by reactions taking place in each of
these reactors.

At the top of the stabilizer residual hydrogen and C 1 to C4 are withdrawn as condenser
products, which are then sent to gas processing, Part of the liquid product (C 3 and C4) is
returned from the reflux drum back to the stabilizer. The main product of the column is
stabilized reformate, which is sent to the gasoline blending plant.

A slight modification to the semi-regenerative process is to add an extra reactor to avoid

shutting down the whole unit during regeneration. Three reactors can be running while
the forth is being regenerated. This modified process is called the cyclic fixed bed
process. The temperature and concentration profile in each reactor is as under
Continuous Regenerative (moving bed) Process. (CRR)
This process was introduced by UOP. It produces high octane reformate and high purity
hydrogen on a continuous basis using small amounts of highly active catalyst. The
process has the best of the cyclic reforming process while at the same time avoiding its
drawbacks. In this process, small quantities of catalyst are continuously withdrawn from
an operating reactor, transported to a regeneration unit, regenerated and then returned
to the reactor system.

The most common design involves stacking all reactors ( 3 or 4) on top of one
another.The effluent from each reactor is sent to a common furnace for heating. The
catalyst moves downwards by gravity from the first reactor (R1) to the forth reactor (R4).
The catalyst is sent to the regenerator to burn off the coke and then sent back to the
first reactor R1. The final product from R4 is sent to the stabilizer and gas recovery
section.
 CCR Platforming versus fixed-bed Platforming.

PROCESS VARIABLES

Feed stock: Boiling range of the feed stock is an important parameter which can
be controlled and the maximum ASTM end point of 478K is specified for reformer
reactor charge. This is because 1) hydrocarbons boiling above 478K are known
to form polycyclic aromatics and thus coke, 2) a change in temperature by 13K in
feed ASTM end point costs about 35% of life between ASTM end point ranges of
463-491K for feed. Straight run naphthas are the major feed stocks for reformers.
Feedstocks rich in naphthenes require less severe conditions to reach a product
octane number target or aromatic concentration. Feedstocks that are lean in
naphthenes and correspondingly higher in paraffins require more severe
operating conditions to obtain a specific quality product.

Catalyst type: Chosen to meet refiners yield, activity and stability need

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 primary mechanism to adjust product
octane number is that of adjusting reactor operating temperatures. Typical
reactor inlet temperatures range from 760K to 820K. With the other operating
conditions held constant, a higher reactor inlet temperature results in a higher
product octane number. Higher temperatures also increase operating severity
and cause more rapid catalyst deactivation.
 Pressure: Reactor operating pressure can practically vary from 3.5 to 30 bar
Pressure affects the reformer yield & catalyst stability. Low pressure increases
yield & octane The lower the operating pressure, the higher the reformate and H2
yields. Low operating pressure results in more severe conditions, causing higher
catalyst deactivation rates. The lowest operating pressures are typically only
practised in continuous reforming units.

Space velocity: Space velocity is an important reforming process variable and is

a measure of the contact time between the reactants and the catalyst. It is
expressed as Liquid Hourly Space Velocity (LHSV) i.e. volume per hour of
reactor charge per volume of catalyst. Low space velocity favors aromatic
formation but also promote cracking. Higher space velocity allows less reaction
time. Space velocity affects the temperature required to achieve a desired
product quality. Lower space velocity entails larger catalyst volumes, signifying
that lower temperatures are required to achieve the same product quality. High
space velocity, a more severe condition, results in higher temperature
requirements for the same product quality. Modern commercial reformers usually
operate in an LHSV range of 1-2/h. For a reformer of 90-100 RON, doubling
LHSV requires an increase of 15-20K in reaction inlet temperature.

H2 / HC ratio: Moles of recycle hydrogen / mole of naphtha charge. Hydrogen is

essential in reforming to avoid unwanted side reactions and reduce catalyst
deactivation. Increase H2 partial pressure or increasing the ratio suppresses coke
formation but promotes hydrocracking. Operation at higher H 2/HC must be
balanced with the utility cost associated with recycling the separator gas.
Reformers designed in 1950s used H2/HC ratio of 8-10 and a hydrogen partial
pressure of 19-35 atm. Modern reformers operate in H 2/HC ratio range 2-5 and a
partial hydrogen pressure of 5-11 atm, a change due to highly active catalysts.

RZ Platforming
The RZ Platforming process is a fixed-bed system that is well suited for use in
aromatics production facilities, particularly for those producers who require benzene.
The RZ Platforming process uses the RZ-100 catalyst. The process is built around a
new type of catalyst called RZ-100. RZ-100 is a zeolitic catalyst, activated with platinum
that gives the highest obtainable yields of benzene, and toluene from naphtha
feedstocks. By virtue of its ability to selectively convert the most difficult feed
components (C6 and C7 paraffins) to aromatics, the RZ Platforming process produces
high yields of benzene, toluene and hydrogen. The superior ability of the RZ Platforming
process to handle light, paraffinic feeds and its flexibility to process straight-run naphtha
fractions provide many options for improving aromatics production. The process also
makes hydrogen and can be installed either as a stand-alone new unit or as an addition
to existing aromatics facilities.

The RZ Platforming process is designed to efficiently convert paraffins and naphthenes

to aromatics with as little ring opening or cracking as possible. Although RZ-100 catalyst
is similar in many ways to conventional reforming catalysts, it differs greatly in the
production of light aromatics benzene and toluene. The selectivity of conventional
reforming catalysts for benzene and toluene is significantly lower than for the C8
aromatics. By comparison, the selectivity of the RZ-100 catalyst for light aromatics is
vastly improved. This improved selectivity can be illustrated by comparing its aromatics
selectivity to that of low-pressure CCR Platforming catalyst.

Process description

The RZ Platforming unit configuration is similar to other Fixed Bed reforming units.
Treated naphtha feed is combined with recycle hydrogen gas and heat exchanged
against reactor effluent. The combined feed is then raised to reaction temperature in the
charge heater and sent to the reactors. Radial-flow reactors are arranged in a
conventional side-by-side flow scheme. The predominant reactions are endothermic, so
an interheater is used between each reactor to reheat the charge to reaction
temperature. Flue gas from the fired heaters is typically used to generate high pressure
steam, but other heat integration options are available. The effluent from the last reactor
is heat exchanged against combined feed, cooled and split into vapor and liquid
products in a separator. The vapor phase is rich in hydrogen and a portion of the gas is
compressed and recycled back to the reactors. The hydrogen-rich net gas is
compressed and charged together with the separator liquid to the product recovery
section. This section is optimized to provide location specific required performance. The
liquid product from the recovery section is sent to a stabilizer where light hydrocarbons
are removed from the C6 + aromatic product. RZ-100 catalyst deactivates over time at
reaction conditions. Units can be designed to have cycle lengths from 8 to 12 months.
UOP provides efficient ex-situ catalyst regeneration facilities for rejuvenation of RZ-100
catalyst.