CATALYTIC REFORMING

INTRODUCTION
• Catalytic reforming is a chemical process used in petroleum refineries to
convert naphtha, typically having low octane ratings, into high-octane liquid
products called reformates which are components of high-octane gasoline
(also known as petrol).

• Basically, the process re-arranges or re-structures the hydrocarbon

molecules in the naphtha feed stocks as well as breaking some of the
molecules into smaller molecules.

• The overall effect is that the product reformate contains hydrocarbons with
more complex molecular shapes having higher octane values than the
hydrocarbons in the naphtha feedstock.

• In addition to producing reformate, catalytic reforming is also a primary

source of aromatics used in the petrochemical industry (BTX: benzene,
toluene, and xylenes).
• The process separates some hydrogen molecules from the hydrocarbon
molecules and produces very significant amounts of byproduct hydrogen for
use in a number of the other processes involved in a modern petroleum
processing refinery. Other byproducts are small amounts of methane,
ethane, propane and butanes.

• This process is quite different from and not to be confused with the catalytic
steam reformer process used industrially to produce various products such
as hydrogen, ammonia and methanol from natural gas, naphtha or other
petroleum-derived feed stocks.
HISTORY

• Universal Oil Products (also known as UOP) is a multi-national company

developing and delivering technology to the petroleum refining, natural gas
processing, petrochemical production and other manufacturing industries.

• In the 1940s, an eminent research chemist named Vladimir Haensel

working for UOP developed a catalytic reforming process using a catalyst
containing platinum.

• Haensel's process was subsequently commercialized by UOP in 1949 for

producing a high octane gasoline from low octane naphthas and the UOP
process became known as the Platforming process.

• The first Platforming unit was built in 1949 at the refinery of the Old Dutch
Refining Company in Muskegon, Michigan.
HISTORY

• In the years since then, many other versions of the process have been developed by some
of the major oil companies and other organizations.

• Today, the large majority of gasoline produced worldwide is derived from the catalytic
reforming process.

• To name a few of the other catalytic reforming versions that were developed, all of
which utilized a platinumand/or a rhenium catalyst

• Rheniforming: Developed by Chevron Oil Company.

• Powerforming: Developed by Esso Oil Company, now known as ExxonMobil.
• Magnaforming: Developed by Engelhard Catalyst Company and Atlantic Richfield Oil
Company. (ARCO).
• Ultraforming: Developed by Standard Oil of Indiana, now a part of the British
Petroleum Company.
• Houdriforming: Developed by the Houdry Process Corporation.
• CCR Platforming: A Platforming version, designed for continuous catalyst regeneration,
developed by UOP.
• Octanizing: A catalytic reforming version developed by Axens, a subsidiary of Institut
Français du Petrole (IFP), designed for continuous catalyst regeneration.
• What are aromatic hydrocarbons?

• Aromatic hydrocarbons make up 20-30% of each gallon of gasoline.

• The most common aromatic hydrocarbons include benzene, toluene, ethylbenzene, and
xylene (BTEX).
• Benzene is the most hazardous and is a known carcinogen. Whereas, toluene and xylene
convert to benzene in the combustion process and contribute to the formation of ozone
smog.
• BTEX is a primary source of ultrafine particulate matter (PM) or ultrafine emissions

• Why do we use aromatic hydrocarbons?

• Aromatic hydrocarbons are added to gasoline to increase the octane rating of an engine,
which leads to better engine performance and increased fuel efficiency.

• The Health Hazards of Aromatic Hydrocarbons

• Ultrafine PM are small enough to penetrate blood cells and travel to the body’s organs
• Some possible adverse health effects include an increased risk of asthma, respiratory
disease, reduced lung development and function in children, cardiovascular disease in
adults, and cancer.
• Despite all of these potential health effects, the U.S. Environmental Protection Agency
does not regulate ultrafine PM and these hazardous aromatic hydrocarbons.
• CHEMISTRY

• Before describing the reaction chemistry of the catalytic reforming process as used
in petroleum refineries, the typical naphthas used as catalytic reforming feed stocks
will be discussed.

Typical naphtha feedstocks

• A petroleum refinery includes many unit processes and unit operations. The first
unit process in a refinery is the crude oil distillation unit. The overhead liquid
distillate from that unit is called "naphtha" and will become a major component of
the refinery's gasoline (petrol) product after it is further processed through a
catalytic hydrodesulfurization unit to remove sulfur-containing hydrocarbons and a
catalytic reformer to reform its hydrocarbon molecules into more complex
molecules with a higher octane rating value.

• The naphtha is a mixture of very many different hydrocarbon compounds. It has an

initial boiling point of about 35 °C and a final boiling point of about 200 °C, and it
contains paraffin, naphthene (cyclic paraffin) and aromatic hydrocarbons ranging
from those containing four to those containing about 10 or 11 carbonatoms.
• The naphtha from the crude oil distillation is often further distilled to produce a
"light" naphtha containing most (but not all) of the hydrocarbons with six or fewer
carbon atoms and a "heavy" naphtha (i.e., dehexanized naphtha) containing most
(but not all) of the hydrocarbons with more than six carbon atoms.

• The heavy naphtha has an initial boiling point of about 140 to 150 °C and a final
boiling point of about 190 to 205 °C.

• The naphthas derived from the distillation of crude oils are referred to as "straight-
run" naphthas.

• It is the straight-run heavy naphtha that is usually processed in a catalytic reformer

because the light naphtha has molecules with 6 or less carbon atoms which, when
reformed, tend to crack into butane and lower molecular weight hydrocarbons which
are not useful as high-octane gasoline blending components.

• Also, the molecules with 6 carbon atoms tend to form aromatics which is
undesirable because governmental environmental regulations in a number of
countries limit the amount of aromatics (most particularly benzene) that gasoline
may contain.
• It should be noted that there are a great many petroleum crude oil sources
worldwide and each crude oil has its own unique composition or assay. Also, not all
refineries process the same crude oils and each refinery produces its own straight-
run naphthas with their own unique initial and final boiling points. In other words,
naphtha is a generic term rather than a specific term.

• The table just below lists some fairly typical straight-run heavy naphtha feedstocks,
available for catalytic reforming, derived from various crude oils. It can be seen that
they differ significantly in their content of paraffins, naphthenes and aromatics:

• Some refinery naphthas include olefinic hydrocarbons, such as naphthas derived

from the fluid catalytic cracking and coking processes used in many refineries.
Some refineries may also desulfurize and catalytically reform those naphthas.

• However, for the most part, catalytic reforming is mainly used on the straight-run
heavy naphthas, such as those in the above table, derived from the distillation of
crude oils.
• THE REACTION CHEMISTRY

• There are a good many chemical reactions that occur in the catalytic reforming
process, all of which occur in the presence of a catalyst and a high partial pressure
of hydrogen.

• Depending upon the type or version of catalytic reforming used as well as the
desired reaction severity, the reaction conditions range from temperatures of about
495 to 525 °C and from gauge pressures of about 5 to 45 atmospheres.

• The commonly used catalytic reforming catalysts contain noble metals such as
platinum and/or rhenium, which are very susceptible to poisoning by sulfur and
nitrogen compounds.

• Therefore, the naphtha feedstock to a catalytic reformer is always pre-processed in a

hydrodesulfurization unit which removes both the sulfur and the nitrogen
compounds.
• The four major catalytic reforming reactions are:

1. The dehydrogenation of naphthenes to convert them into aromatics as exemplified

in the conversion methylcyclohexane (a naphthene) to toluene (an aromatic), as
shown below:

2. The isomerization of normal paraffins to isoparaffins as exemplified in the

conversion of normal octane to 2,5-Dimethylhexane (an isoparaffin), as
shown below:
3. The dehydrogenation and aromatization of paraffins to aromatics (commonly called
dehydrocyclization) as exemplified in the conversion of normal heptane to toluene,
as shown below:

• The hydrocracking of paraffins into smaller molecules as exemplified by the

cracking of normal heptane into isopentane and ethane, as shown below:
• The hydrocracking of paraffins is the only one of the above four major reforming
reactions that consumes hydrogen.

• The isomerization of normal paraffins does not consume or produce hydrogen.

• However, both the dehydrogenation of naphthenes and the de-hydrocyclization of

paraffins produce hydrogen.

• The overall net production of hydrogen in the catalytic reforming of petroleum

naphthas (In the United States customary units) that is equivalent to 300 to 1200
standard cubic feet of hydrogen gas (at 60 °F and one atmosphere) per barrel of
liquid naphtha feedstock.

• In many petroleum refineries, the net hydrogen produced in catalytic reforming

supplies a significant part of the hydrogen used elsewhere in the refinery (for
example, in hydrodesulfurization processes).
• TYPES OF CATALYTIC REFORMING PROCESSES

• Catalytic reforming processes are commonly classified according to the

frequency and mode of catalyst regeneration, into
• (1) semi-regenerative,
• (2) cyclic regeneration, and
• (3) continuous regeneration.

• The main difference among the three types of processes is the need of unit
shutdown for catalyst regeneration in the case of a semi-regenerative
process,

• the use of an additional swing or spare reactor for catalyst regeneration for
the cyclic process.

• and catalyst replacement during normal operation for the continuous

regeneration type.
• The most used process worldwide is the semi regenerative type, followed by
continuous regeneration and by the less common cyclic regeneration.

• Currently, most catalytic reformers are designed with continuous regeneration, and
the former semi regenerative plants are being revamped to operate as continuous
regeneration.
• Semi regenerative

• A semi-regenerative catalytic reforming process usually has three or four reactors in

series with a fixed-bed catalyst system and operates continuously (cycle length)
from six months to one year.
• During this period, the activity of the catalyst diminishes due to coke deposition,
provoking a decrease in aromatics yield and in hydrogen gas purity.
• To minimize the catalyst deactivation rate, the semiregenerative units operate at
high pressure (200 to 300 psig).
• To compensate for catalyst activity decline and to keep conversion more or less
constant, the reactor temperatures are increased continuously. When the end- of-
cycle reactor temperatures are reached, the unit is shutdown and the catalyst is in
situ regenerated.
• A catalyst cycle ends when the reforming unit is unable to meet its process
objectives: octane and yield reformate. Catalyst regeneration is carried out with air
as the source of oxygen.
• A catalyst can be regenerated five to ten times before it is removed and replaced.
• Cyclic Regeneration
• Apart from the catalytic reforming reactors, the cyclic regeneration process
has an additional swing reactor, which is used when the fixed-bed catalyst of
any of the regular reactors needs regeneration.
• The reactor with the regenerated catalyst then becomes the spare reactor.
• By this means, the reforming process maintains continuous operation.
Operating at lower pressure (-200 psig) allows the cyclic regeneration
process to achieve higher reformate yield and hydrogen production.
• Compared with the semi regenerative type, in the cyclic regeneration
process the overall catalyst activity varies much less with time, so that
conversion and hydrogen purity are kept more or less constant during the
entire operation.
• The main disadvantage of this type of catalytic reforming is the complex
nature of the reactor switching policy, requiring high safety precautions.
Also, to make switches between reactors possible, they need to be of the
same maximal size.
• Continuous Regeneration

• The deficiencies in cyclic regeneration reforming are solved by a low-

pressure (50 psig) continuous regeneration process, which is characterized
by high catalyst activity with reduced catalyst requirements, producing more
uniform reformate of higher aromatic content and high hydrogen purity.

• This type of process uses moving-bed reactor design, in which the reactors
are stacked.
• The catalyst bed moves by gravity flow from top to bottom of the stacked
reactors. The spent catalyst is withdrawn from the last reactor and sent to
the top of the regenerator to burn off the coke.
• The transport of catalyst between reactors and regenerator is done by the
gas lift method.
• During normal operation, small quantities of catalyst are withdrawn
continuously. Fresh or regenerated catalysts are added to the top of the first
reactor to maintain a constant inventory of catalyst.
• Continuous Regeneration

• In parallel with bimetallic catalyst improvements and other process and regeneration
advances, UOP began to develop the CCR Platforming™ process (Figure 5.7).

• In the CCR Platforming unit, partially aged catalyst in the reactors is continuously
replaced with catalyst that has been freshly regenerated in an external
regenerator(CCRsection) to maintain a low average age for the reactor catalyst.

• Thus, the high selectivity and high activity characteristics associated with new
catalyst can be maintained at significantly higher severities than with the SR
Platforming process.

• For example, a SR Platforming unit operates at a severity that steadily builds coke
up on the catalyst surface over the length of a cycle (6–18 months), at which point
the unit is shut down and the catalyst regenerated. Throughout the cycle, yields
decline.
• Instead, in a modern CCR Platforming unit, the catalyst is regenerated
approximately every three to seven days and the yield does not decline.
• The ability to continuously regenerate a controlled quantity of catalyst is the
significant innovation of the CCR Platforming unit.

• The catalyst flows by gravity from the last reactor into a catalyst collector vessel.

• The catalyst is lifted by either nitrogen or hydrogen lifting gas to a catalyst hopper
above the regeneration tower.

• Catalyst then flows to the regeneration tower, where the catalyst is reconditioned.

• Regenerated catalyst is returned to the top of the reactor stack by a transfer system
similar to that used in the reactor-to-regenerator transfer.

• Thus, the reactors are continuously supplied with freshly regenerated catalyst, and
product yields are maintained at fresh catalyst level.
• The regeneration and reactor sections of the unit are easily isolated to permit a
shutdown of the regeneration system for normal inspection or maintenance without
interrupting of the Platforming operation.
• CATALYST

• The main characteristics of a catalyst other than its physical and mechnaical
properties are:

The Activity
• Catalyst ability to increase the rate of desired reactions

The selectivity
Catalyst ability to favor desirable reactions
Practically measured by the C5+ reformate and hydrogen yields

The stability
• Change of catalyst performance (activity, selectivity) with time.
• Caused chiefly by coke deposit and by traces of metals in feed
• Measured by the amount feed treated per unit weight of catalyst. C5+ reformate
yield is also an indirect measure of stability.
• CATALYST

• Typical catalysts that consist of platinum supported on alumina are bifunctional in

that separate and distinct reactions occur on the platinum site and on the alumina.

• The platinum typically performs dehydrogenation and hydrogenolysis, while the

acidic alumina isomerizes, cyclizes, and cracks.

• The platinum must be dispersed over the alumina surface such that the maximum
number of active sites for dehydrogenation is available.

• The interaction of the platinum with the alumina surface is such that the platinum
clusters are relatively immobile and do not agglomerate during reforming.

• Sulfidation of the platinum is sometimes used to partially poison the platinum, or

reduce its activity; this has the beneficial effect of reducing a major portion of the
hydrogenolysis, or metal-catalyzed cracking reactions. Liquid product yields are
improved and the light gas production, particularly methane, is reduced.
• Chloride is added to promote acidity to Alumina.

• A typical fixed bed catalyst life cycle may be a year or longer.

• Modifiers are added to reduce the effect of coke buildup and to lengthen the catalyst
cycle length, either by hydrogenating the coke to a less graphitic species (6) or by
cracking the coke precursors (7). Elements that are commonly added to the catalysts
are rhenium and, to a lesser extent, iridium.

• In moving bed units (8) the catalyst flows through the reactors and is regenerated
continually in a separate regeneration vessel that is part of the reactor–regenerator
loop.

• Process conditions are much more severe, thus shortening catalyst life and requiring
regeneration cycles of only a few days. In moving bed catalysts elements are added,
such as tin and germanium, to increase liquid, aromatic, and hydrogen yields by
reducing the activity of the platinum for hydrogenolysis or metal-catalyzed cracking
reactions.
• Deactivation mechanisms for reforming catalysts include coking, poisoning, and
agglomeration of the platinum. Under normal conditions coke accumulates on the
catalyst.

• In a fixed bed or SR unit, this coke will deactivate the catalyst such that, in time, the
temperature limit of the reforming unit will be reached, or the selectivity to desired
products is too much reduced, or the octane of the liquid product is declining.

• When this occurs, the refiner will shut down the process unit and regenerate the
catalyst to return it to its original state.

• In a moving bed unit, some of the catalyst is continually being regenerated outside
the process and returned to the reactors. High selectivity and activity are maintained.

• The actual chemistry and steps for regeneration for all process units are very similar.
• In the following discussion, catalyst regeneration for a SR reformer is described.

• For cyclic or continuous reformers, plant shutdown and start-up are unnecessary and
the remaining steps are accomplished in equipment outside the process stream.
• The objective of regeneration is to return the catalyst to its initial, fresh state. If the
regeneration is successful, there is no difference between fresh and regenerated
catalyst.

• To do this, the coke must be burnt off the catalyst, the platinum should be well
dispersed and in a reduced state, and the acidity should be properly adjusted through
chloride adsorption.

• In order to conduct a regeneration, the heater temperatures and feed rates are
reduced gradually. The circulation of recycle gas is continued to strip hydrocarbons
from the catalyst, leaving only coke.

• If the coke is to be burnt in the unit, higher temperatures are maintained and the
coke burning procedure is initiated.

• Since coked catalyst is often pyrophoric(liable to ignite spontaneously on exposure

to air), nitrogen blanketing is often used to protect the catalyst from air contact and
combustion.
• The coke burning step must be carefully monitored. The combustion of coke to
carbon dioxide and water is exothermic, and the oxygen concentration must be kept
low to limit the reaction and temperature rise.

• Excessive temperature can cause agglomeration of the platinum or, in more extreme
cases, can cause the alumina to change.

• Due to the need to gradually burn coke, the carbon burn is usually the most time-
consuming part of a regeneration.

• Coke burning is usually done in the range of 400–500◦C, and at oxygen

concentrations initially in the 1–2 mol% range.

• Oxygen content and temperature are often increased during burning to ensure that
all coke has been combusted by the end of the burn.

• Oxygen consumption is monitored to determine the total amount of coke combusted

and the extent of the burn.
• Since platinum can agglomerate even at relatively moderate exothermic conditions,
the platinum must be redispersed after the carbon burn.

• The temperature is first increased to approximately 500◦C, oxygen content to

approximately 5–6 mol%, and chlorine or an organic chloride that breaks down to
HCl and Cl2 is injected into the air/nitrogen stream.

• Platinum oxychlorides or chlorides form that redisperse platinum over the alumina
surface, ensuring that almost all the platinum is exposed for reaction.

• This also adds chloride to the catalyst to enhance its acidity.

• Finally, the last step in the regeneration process is the reduction of the metals on the
catalyst and sulfiding, if necessary. This is done in a dry hydrogen atmosphere.

• The temperatures required for reduction, greater than 350◦C, high moisture levels
can lead to platinum agglomeration. Since water is formed in the reduction process
as platinum oxide is reduced to platinum metal, water is drained from the unit
during reduction.

• The reduction hydrogen is recirculated at as high a rate as possible in order

• to minimize moisture content.

• Sulfiding is typically done by injection of H2S or of an organic sulfide into the unit
at the end of reduction.

• Sulfiding is continued until the specified sulfur level is reached or until sulfur is no
longer adsorbed by the catalyst and is detected at the outlet of the catalyst bed.