Catalytic reforming

Catalytic reforming is a chemical process used to convert petroleum refinery naphthas distilled from crude oil
(typically having low octane ratings) into high-octane liquid products called reformates, which are premium
blending stocks for high-octane gasoline. The process converts low-octane linear hydrocarbons (paraffins) into
branched alkanes (isoparaffins) and cyclic naphthenes, which are then partially dehydrogenated to produce
high-octane aromatic hydrocarbons. The dehydrogenation also produces significant amounts of byproduct
hydrogen gas, which is fed into other refinery processes such as hydrocracking. A side reaction is
hydrogenolysis, which produces light hydrocarbons of lower value, such as methane, ethane, propane and
butanes.

In addition to a gasoline blending stock, reformate is the main source of aromatic bulk chemicals such as
benzene, toluene, xylene and ethylbenzene which have diverse uses, most importantly as raw materials for
conversion into plastics. However, the benzene content of reformate makes it carcinogenic, which has led to
governmental regulations effectively requiring further processing to reduce its benzene content.

This process is quite different from and not to be confused with the catalytic steam reforming process used
industrially to produce products such as hydrogen, ammonia, and methanol from natural gas, naphtha or other
petroleum-derived feedstocks. Nor is this process to be confused with various other catalytic reforming
processes that use methanol or biomass-derived feedstocks to produce hydrogen for fuel cells or other uses.

Contents
History
Chemistry
Typical naphtha feedstocks
The reaction chemistry
Model reactions using lumping technique
Process description
Catalysts and mechanisms
Weaknesses and Competition
Economics
References
External links

History
In the 1940s, Vladimir Haensel,[1] a research chemist working for Universal Oil Products (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 become known as the Platforming process.[2] The first Platforming unit was built in 1949 at the
refinery of the Old Dutch Refining Company in Muskegon, Michigan.
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 platinum
and/or a rhenium catalyst:

Rheniforming: Developed by Chevron Oil Company.

CCR Platforming: A Platforming version, designed for continuous catalyst regeneration,
developed by Universal Oil Products (UOP).
Powerforming: Developed by Esso Oil Company, currently known as ExxonMobil.
Magnaforming: Developed by Engelhard and Atlantic Richfield Oil Company.
Ultraforming: Developed by Standard Oil of Indiana, now a part of the British Petroleum
Company.
Houdriforming: Developed by the Houdry Process Corporation.
Octanizing: A catalytic reforming version developed by Axens, a subsidiary of Institut francais
du petrole (IFP), designed for continuous catalyst regeneration.

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

Typical naphtha feedstocks

A petroleum refinery includes many unit operations and unit processes. The first unit operation in a refinery is
the continuous distillation of the petroleum crude oil being refined. The overhead liquid distillate is called
naphtha and will become a major component of the refinery's gasoline (petrol) product after it is further
processed through a catalytic hydrodesulfurizer 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 paraffins) and
aromatic hydrocarbons ranging from those containing 6 carbon atoms to those containing about 10 or 11
carbon atoms.

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 6 or fewer carbon atoms and a "heavy" naphtha containing most
(but not all) of the hydrocarbons with more than 6 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 fewer 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.[3][4][5]

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:

Typical Heavy Naphtha Feedstocks

Crude oil name Barrow Island Mutineer-Exeter CPC Blend Draugen

Location Australia[6] Australia[7] Kazakhstan[8] North Sea[9]
Initial boiling point, °C 149 140 149 150
Final boiling point, °C 204 190 204 180
Paraffins, liquid volume % 46 62 57 38
Naphthenes, liquid volume % 42 32 27 45
Aromatics, liquid volume % 12 6 16 17

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 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 pressures of about 5 to 45 atm.[10][11]

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. Most catalysts require both sulphur and nitrogen content to be lower than 1 ppm.

The four major catalytic reforming reactions are:[12]

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:

4: The hydrocracking of paraffins into smaller molecules as exemplified by the cracking of

normal heptane into isopentane and ethane, as shown below:

During the reforming reactions, the carbon number of the reactants remains unchanged, except for
hydrocracking reactions which break down the hydrocarbon molecule into molecules with fewer carbon
atoms.[11] 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 dehydrocyclization of paraffins produce hydrogen. The
overall net production of hydrogen in the catalytic reforming of petroleum naphthas ranges from about 50 to
200 cubic meters of hydrogen gas (at 0 °C and 1 atm) per cubic meter of liquid naphtha feedstock. In the
United States customary units, that is equivalent to 300 to 1200 cubic feet of hydrogen gas (at 60 °F and 1
atm) per barrel of liquid naphtha feedstock.[13] 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). The hydrogen is also necessary in order to hydrogenolyze any polymers that
form on the catalyst.

In practice, the higher the content of naphtenes in the naphtha feedstock, the better will be the quality of the
reformate and the higher the production of hydrogen. Crude oils containing the best naphtha for reforming are
typically from Western Africa or the North Sea, such as Bonny light oil or Norwegian Troll.

Model reactions using lumping technique

Owing to too many components in catalytic reforming process feedstock, untraceable reactions and the high
temperature range, the design and simulation of catalytic reformer reactors is accompanied by complexities.
The lumping technique is used extensively for reducing complexities so that the lumps and reaction pathways
that properly describe the reforming system and kinetic rate parameters do not depend on feedstock
composition.[11] In one of the recent works, naphtha is considered in terms of 17 hydrocarbon fractions with
15 reactions in which C1 to C5 hydrocarbons are specified as light paraffins and the C6 to C8+ naphtha cuts
are characterized as isoparaffins, normal paraffins, naphthenes and aromatics.[11] Reactions in catalytic
naphtha reforming are elementary and Hougen-Watson Langmuir-Hinshelwood type reaction rate expressions
are used to describe the rate of each reaction. Rate equations of this type explicitly account for the interaction
of chemical species with catalyst and contain denominators in which terms characteristic of the adsorption of
reacting species are presented.[11]
Process description
The most commonly used type of catalytic reforming unit has three reactors, each with a fixed bed of catalyst,
and all of the catalyst is regenerated in situ during routine catalyst regeneration shutdowns which occur
approximately once each 6 to 24 months. Such a unit is referred to as a semi-regenerative catalytic reformer
(SRR).

Some catalytic reforming units have an extra spare or swing reactor and each reactor can be individually
isolated so that any one reactor can be undergoing in situ regeneration while the other reactors are in operation.
When that reactor is regenerated, it replaces another reactor which, in turn, is isolated so that it can then be
regenerated. Such units, referred to as cyclic catalytic reformers, are not very common. Cyclic catalytic
reformers serve to extend the period between required shutdowns.

The latest and most modern type of catalytic reformers are called continuous catalyst regeneration (CCR)
reformers. Such units are defined by continuous in-situ regeneration of part of the catalyst in a special
regenerator, and by continuous addition of the regenerated catalyst to the operating reactors. As of 2006, two
CCR versions available: UOP's CCR Platformer process[14] and Axens' Octanizing process.[15] The
installation and use of CCR units is rapidly increasing.

Many of the earliest catalytic reforming units (in the 1950s and 1960s) were non-regenerative in that they did
not perform in situ catalyst regeneration. Instead, when needed, the aged catalyst was replaced by fresh
catalyst and the aged catalyst was shipped to catalyst manufacturers to be either regenerated or to recover the
platinum content of the aged catalyst. Very few, if any, catalytic reformers currently in operation are non-
regenerative.

The process flow diagram below depicts a typical semi-regenerative catalytic reforming unit.

Schematic diagram of a typical semi-regenerative catalytic reformer unit in a petroleum refinery

The liquid feed (at the bottom left in the diagram) is pumped up to the reaction pressure (5–45 atm) and is
joined by a stream of hydrogen-rich recycle gas. The resulting liquid–gas mixture is preheated by flowing
through a heat exchanger. The preheated feed mixture is then totally vaporized and heated to the reaction
temperature (495–520 °C) before the vaporized reactants enter the first reactor. As the vaporized reactants flow
through the fixed bed of catalyst in the reactor, the major reaction is the dehydrogenation of naphthenes to
aromatics (as described earlier herein) which is highly endothermic and results in a large temperature decrease
between the inlet and outlet of the reactor. To maintain the required reaction temperature and the rate of
reaction, the vaporized stream is reheated in the second fired heater before it flows through the second reactor.
The temperature again decreases across the second reactor and the vaporized stream must again be reheated in
the third fired heater before it flows through the third reactor. As the vaporized stream proceeds through the
three reactors, the reaction rates decrease and the reactors therefore become larger. At the same time, the
amount of reheat required between the reactors becomes smaller. Usually, three reactors are all that is required
to provide the desired performance of the catalytic reforming unit.

Some installations use three separate fired heaters as shown in the schematic diagram and some installations
use a single fired heater with three separate heating coils.

The hot reaction products from the third reactor are partially cooled by flowing through the heat exchanger
where the feed to the first reactor is preheated and then flow through a water-cooled heat exchanger before
flowing through the pressure controller (PC) into the gas separator.

Most of the hydrogen-rich gas from the gas separator vessel returns to the suction of the recycle hydrogen gas
compressor and the net production of hydrogen-rich gas from the reforming reactions is exported for use in the
other refinery processes that consume hydrogen (such as hydrodesulfurization units and/or a hydrocracker
unit).

The liquid from the gas separator vessel is routed into a fractionating column commonly called a stabilizer.
The overhead offgas product from the stabilizer contains the byproduct methane, ethane, propane and butane
gases produced by the hydrocracking reactions as explained in the above discussion of the reaction chemistry
of a catalytic reformer, and it may also contain some small amount of hydrogen. That offgas is routed to the
refinery's central gas processing plant for removal and recovery of propane and butane. The residual gas after
such processing becomes part of the refinery's fuel gas system.

The bottoms product from the stabilizer is the high-octane liquid reformate that will become a component of
the refinery's product gasoline. Reformate can be blended directly in the gasoline pool but often it is separated
in two or more streams. A common refining scheme consists in fractionating the reformate in two streams, light
and heavy reformate. The light reformate has lower octane and can be used as isomerization feedstock if this
unit is available. The heavy reformate is high in octane and low in benzene, hence it is an excellent blending
component for the gasoline pool.

Benzene is often removed with a specific operation to reduce the content of benzene in the reformate as the
finished gasoline has often an upper limit of benzene content (in the UE this is 1% volume). The benzene
extracted can be marketed as feedstock for the chemical industry.

Catalysts and mechanisms

Most catalytic reforming catalysts contain platinum or rhenium on a silica or silica-alumina support base, and
some contain both platinum and rhenium. Fresh catalyst is chlorided (chlorinated) prior to use.

The noble metals (platinum and rhenium) are considered to be catalytic sites for the dehydrogenation reactions
and the chlorinated alumina provides the acid sites needed for isomerization, cyclization and hydrocracking
reactions.[12] The biggest care has to be exercised during the chlorination. Indeed, if not chlorinated (or
insufficiently chlorinated) the platinum and rhenium in the catalyst would be reduced almost immediately to
metallic state by the hydrogen in the vapour phase. On the other hand, an excessive chlorination could depress
excessively the activity of the catalyst.

The activity (i.e., effectiveness) of the catalyst in a semi-regenerative catalytic reformer is reduced over time
during operation by carbonaceous coke deposition and chloride loss. The activity of the catalyst can be
periodically regenerated or restored by in situ high temperature oxidation of the coke followed by chlorination.
As stated earlier herein, semi-regenerative catalytic reformers are regenerated about once per 6 to 24 months.
The higher the severity of the reacting conditions (temperature), the higher the octane of the produced
reformate but also the shorter the duration of the cycle between two regenerations. Catalyst's cycle duration is
also very dependent on the quality of the feedstock. However, independently of the crude oil used in the
refinery, all catalysts require a maximum final boiling point of the naphtha feedstock of 180 °C.

Normally, the catalyst can be regenerated perhaps 3 or 4 times before it must be returned to the manufacturer
for reclamation of the valuable platinum and/or rhenium content.[12]

Weaknesses and Competition

The sensitivity of catalytic reforming to contamination by sulfur and nitrogen requires hydrotreating the
naphtha before it enters the reformer, adding to the cost and complexity of the process. Dehydrogenation, an
important component of reforming, is a strongly endothermic reaction, and as such, requires the reactor vessel
to be externally heated. This contributes both to costs and the emissions of the process. Catalytic reforming has
a limited ability to process naphthas with a high content of normal paraffins, e.g. naphthas from the gas-to-
liquids (GTL) units. The reformate has a much higher content of benzene than is permissible by the current
regulations in many countries. This means that the reformate should either be further processed in an aromatics
extraction unit, or blended with appropriate hydrocarbon streams with low content of aromatics. Catalytic
reforming requires a whole range of other processing units at the refinery (apart from the distillation tower, a
naphtha hydrotreater, usually an isomerization unit to process light naphtha, an aromatics extraction unit, etc.)
which puts it out of reach for smaller (micro-)refineries.

Main licensors of catalytic reforming processes, UOP and Axens, constantly work on improving the catalysts,
but the rate of improvement seems to be reaching its physical limits. This is driving the emergence of new
technologies to process naphtha into gasoline by companies like Chevron Phillips Chemical (Aromax (http://w
ww.cpchem.com/en-us/rnt/licensing/aromaxtech/pages/process.aspx) [16]) and NGT Synthesis (Methaforming
(https://www.ngt-synthesis.com/technology/) [16], [17]).

Economics
Catalytic reformation is profitable in that it converts long-chain hydrocarbons, for which there is limited
demand despite high supply, into short-chained hydrocarbons, which, due to their uses in petrol fuel, are in
much greater demand. It can also be used to improve the octane rating of short-chained hydrocarbons by
aromatizing them.[18]

References
1. A Biographical Memoir of Vladimir Haensel (https://wayback.archive-it.org/all/2008030915514
6/http://newton.nap.edu/html/biomems/vhaensel.pdf) written by Stanley Gembiki, published by
the National Academy of Sciences in . 2006.
2. Platforming described on UOP's website (http://www.uop.com/refining/1030.html) Archived (http
s://web.archive.org/web/20061230130259/http://www.uop.com/refining/1030.html) December
30, 2006, at the Wayback Machine
3. Canadian regulations on benzene in gasoline (http://www.ec.gc.ca/CEPARegistry/regulations/d
etailReg.cfm?intReg=1) Archived (https://web.archive.org/web/20041012052626/http://www.ec.
gc.ca/CEPARegistry/regulations/detailReg.cfm?intReg=1) 2004-10-12 at the Wayback
Machine
 4. United Kingdom regulations on benzene in gasoline (http://www.ukpia.com/industry_issues/en
vironment_air_quality_health_safety/benzene_in_petrol.aspx) Archived (https://web.archive.or
g/web/20061123043249/http://www.ukpia.com/industry_issues/environment_air_quality_health
_safety/benzene_in_petrol.aspx) November 23, 2006, at the Wayback Machine
5. USA regulations on benzene in gasoline (https://www.washingtonpost.com/wp-dyn/content/arti
cle/2006/03/01/AR2006030102113.html)
6. "Barrow Island crude oil assay" (https://web.archive.org/web/20080309155147/http://www.sant
os.com/library/barrow_crude.pdf) (PDF). Archived from the original (http://www.santos.com/libra
ry/barrow_crude.pdf) (PDF) on 2008-03-09. Retrieved 2006-12-16.
7. "Mutineer-Exeter crude oil assay" (https://web.archive.org/web/20080309155150/http://www.sa
ntos.com/library/refining_characteristics.pdf) (PDF). Archived from the original (http://www.sant
os.com/library/refining_characteristics.pdf) (PDF) on 2008-03-09. Retrieved 2006-12-16.
8. CPC Blend crude oil assay (http://crudemarketing.chevron.com/overview.asp?cpc)
9. Draugen crude oil assay (http://www.statoil.com/STATOILCOM/crude/svg02659.nsf/UNID/C9A
C3EF9CE76B0DFC1256B5600528D6D/$FILE/Dra4kv02.pdf) Archived (https://web.archive.or
g/web/20071128055711/http://www.statoil.com/STATOILCOM/crude/svg02659.nsf/UNID/C9AC
3EF9CE76B0DFC1256B5600528D6D/%24FILE/Dra4kv02.pdf) November 28, 2007, at the
Wayback Machine
10. OSHA Technical Manual, Section IV, Chapter 2, Petroleum refining Processes (http://www.osh
a.gov/dts/osta/otm/otm_iv/otm_iv_2.html#3) (A publication of the Occupational Safety and
Health Administration)
11. Arani, H. M.; Shirvani, M.; Safdarian, K.; Dorostkar, E. (December 2009). "Lumping procedure
for a kinetic model of catalytic naphtha reforming" (https://doi.org/10.1590/S0104-66322009000
400011). Brazilian Journal of Chemical Engineering. 26 (4): 723–732. doi:10.1590/S0104-
66322009000400011 (https://doi.org/10.1590%2FS0104-66322009000400011). ISSN 0104-
6632 (https://www.worldcat.org/issn/0104-6632).
12. Gary, J.H.; Handwerk, G.E. (1984). Petroleum Refining Technology and Economics (2nd ed.).
Marcel Dekker, Inc. ISBN 0-8247-7150-8.
13. US Patent 5011805, Dehydrogenation, dehydrocyclization and reforming catalyst (http://www.fr
eepatentsonline.com/5011805.html) (Inventor: Ralph Dessau, Assignee: Mobil Oil Corporation)
14. "CCR Platforming" (https://web.archive.org/web/20061109201249/http://www.uop.com/objects/
CCR%20Platforming.pdf) (PDF). uop.com. 2004. Archived from the original (http://www.uop.co
m/objects/CCR%20Platforming.pdf) (PDF) on November 9, 2006.
15. Octanizing Options (http://www.axens.net/upload/news/fichier/ptq_q1_06_octanizing_reformer_
options.pdf) (Axens website)
16. http://subscriber.hydrocarbonpublishing.com/ReviewP/Review3q17catr.pdf
17. http://sk.ru/net/1110056/b/news/archive/2015/07/30/leading-industry-magazine-hydrocarbon-
processing-acknowledges-ngts_2700_-innovation-process.aspx
18. Lichtarowicz, Marek. "Cracking and related refinery" (http://www.essentialchemicalindustry.org/
processes/cracking-isomerisation-and-reforming.html). Retrieved 2017-12-03.

External links
Oil Refinery Processes, A Brief Overview (https://web.archive.org/web/20080309155144/http://
www.processengr.com/ppt_presentations/oil_refinery_processes.pdf)
Colorado School of Mines, Lecture Notes (http://home.comcast.net/~jjechura/CHEN409/09_Ga
soline_Upgrading.pdf) (Chapter 10, Refining Processes, Catalytic Refinery by John Jechura,
Adjunct Professor)
Students' Guide to Refining (http://www.cheresources.com/refining3.shtml) (scroll down to
Platforming)
 Modern Refinery (https://web.archive.org/web/20060927054423/http://www.dct.tudelft.nl/race/e
ducation/smst/smst200303.pdf) Website of Delft University of Technology, Netherlands (use
search function for Reforming)
Major scientific and technical challenges about development of new refining processes (http://w
ww.ifp.fr/IFP/fr/IFP02OGS.nsf/(VNoticesOGST)/AD4A1392D20E5AAEC1256CDE0055399E/$f
ile/decroocq_52n5.pdf?openelement) (IFP website)

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