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Catalytic Naphtha Reforming: January 2006
Catalytic Naphtha Reforming: January 2006
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Abdullah M. Aitani
King Fahd University of Petroleum and Minerals
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To cite this entry: Abdullah M. Aitani . Catalytic Naphtha Reforming. In Encyclopedia of Chemical Processing. Taylor and
Francis: New York, Published online: 12 Dec 2007; 397-406.
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Catalytic Naphtha Reforming
Abdullah M. Aitani
King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
type.[4] The semiregenerative scheme dominates the levels has allowed the semiregenerative units to operate
reforming capacity at about 57% of the total capacity at 14–17 bar with similar cycle lengths obtained at higher
followed by continuous regenerative at 27% and cyclic pressures. It is believed that all reforming licensors have
at 11%. Most grassroots reformers are designed for semiregenerative process design options.[6]
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The research octane number (RON) that can be cyclic processes. Since its introduction in the early
achieved in this process is usually in the range of 85– 1970s, it has gained wide acceptance in refining and
100, depending on an optimization between feedstock petrochemical industries worldwide.
quality, gasoline qualities and quantities required, as In this process, small quantities of catalyst are
well as the operating conditions required to achieve a continuously withdrawn from an operating reactor,
certain planned cycle length (6 mo to 1 yr). The catalyst transported to a regeneration unit, regenerated, and
can be regenerated in situ at the end of an operating returned to the reactor system. In the most common
cycle. Often the catalyst inventory can be regenerated moving-bed design, all the reactors are stacked on
5–10 times before its activity falls below the economic top of one another. The fourth (last) reactor may be
minimum, whereupon it is removed and replaced. set beside the other stacked reactors. The reactor
system has a common catalyst bed that moves as a
column of particles from top to bottom of the reactor
Cyclic (Fully Regenerative) Process
section. Coked catalyst is withdrawn from the last
reactor and sent to the regeneration reactor, where
The cyclic process typically uses five or six fixed cata-
the catalyst is regenerated on a continuous basis. How-
lyst beds, similar to the semiregenerative process, with
ever, the final step of the regeneration, i.e., reduction of
one additional swing reactor, which is a spare reactor.
the oxidized platinum and second metal, takes place in
It can substitute any of the regular reactors in a train
the top of the first reactor or at the bottom of the
while the regular reactor is being regenerated. In this
regeneration train.
way, only one reactor at a time has to be taken out
Fresh or regenerated catalyst is added to the top
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The CCR process is characterized by high catalyst Several commercial reforming processes are available
activity with reduced catalyst requirements, more uni- for license worldwide. A list of reforming processes
form reformate of higher aromatic content, and high with a summary of key process features is presented in
hydrogen purity. The process can achieve and surpass Table 3. Several commercial processes are available,
reforming severities as applied in the cyclic process but dominated by UOP and Axens Technologies for semi-
avoids the drawbacks of the cyclic process. The contin- regenerative and continuous reforming. Other licensors
uous process represents a step change in reforming included Houdry Division, Chevron, Engelhard, Exxon-
technology compared to the semiregenerative and Mobil, and Amoco, but none of them is currently
400 Catalytic Naphtha Reforming
actively licensing.[6] The processes differ in the type maintain a steady-state reforming operation at opti-
of operation (semiregenerative or CCR), catalyst type, mum process conditions: fresh catalyst performance,
catalyst regeneration procedure, and process engineering low reactor pressure, and minimum recycled gas circu-
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The high-efficiency regenerator design resulted in an that are arranged in a conventional side-by-side pat-
increased coke-burning capacity with reduced regen- tern. Interheater is used between each reactor to reheat
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eration severity and complexity. CycleMax regenerator the charge to reaction temperature. Treated naphtha
provided easier operation and enhanced performance feed is combined with recycled hydrogen and sent to
over other regenerator designs. The operation at ultra- the reactor section. The effluent from the last reactor
low pressure (3.4 bar) and the use of low-platinum is heat exchanged against combined feed, cooled, and
catalyst ensured the highest yield of the reformate phase split into vapor and liquid products in a separa-
and aromatic product with more cost-effective process tor. The liquid from the recovery section is sent to
operation. The net gas recovery schemes maximized a stabilizer where light saturates are removed from
the yields of reformate and hydrogen. Moreover, the the C6þ aromatic product. Typical cycle lengths are
new regenerator allowed higher regeneration rates 8–10 mo and the units are designed for efficient in situ
to support the coke generation of the low-pressure catalyst regeneration.
operation and high conversion levels.
UOP has developed the RZ platforming process
Octanizing Process
for high aromatics selectivity, in the range of 80%
or higher. The selectivity of conventional reforming
The Axens octanizing reforming technology is based
for benzene and toluene is significantly lower than for
on Institut Français du Pétrole (IFP) and Procatalyse’s
the C8 aromatics. Although UOP CCR platforming
reforming expertise for the upgrade of various types of
is the most efficient means for producing xylenes from
naphtha to produce high-octane reformate, BTX, and
heavy naphtha fractions, its conversion of C6 and C7
LPG. The reforming process can be supplied in either
paraffins to aromatics is normally below 50%, even
semiregenerative or continuous operation.[9–11] The
at low pressure. In general, RZ platforming configura-
Axens semiregenerative version is a conventional
tion is consistent with other UOP platforming systems.
reforming process in which the catalyst is regenerated
The process employs adiabatic, radial-flow reactors
in situ at the end of each cycle. The operating pressure
of this process is in the range of 12–25 bar with low-
pressure drop in the hydrogen loop. The product
Table 4 Typical yields of UOP semiregenerative and CCR
units for a Middle East naphtha feed RON-clear is in the range 90–100. Trimetallic catalyst
formulations for semiregenerative applications offer
Parameter Semiregenerative CCR
higher selectivity and stability.
Catalyst type R-72 R-274 The decrease in the reformate yield during the run
Stream factor (day=yr) 330 360 of the semiregenerative version (in spite of improved
Pressure (kPa) 1380 345 catalyst stability) has led Axens to develop a catalyst
Yield moving-bed system that allows continuous regene-
ration of the catalyst. The octanizing process is an
Hydrogen (scfd) 1270 1690
advanced design that reflects the results of several dec-
C5þ (wt%) 85.3 91.6 ades of research and development efforts. The heart of
RON-clear 100 100 the technology lies in its original catalyst circulation
(From Ref.[8].) and CCR systems. A schematic flow diagram of the
402 Catalytic Naphtha Reforming
octanizing process is presented in Fig. 2.[12] The overall petrochemical complement to the octanizing process.
process comprises the following: The technology employs an advanced catalyst formu-
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aromatics, without provision for catalyst regeneration. Alternatively, the process may be operated to give high
However, operation at high severity requires frequent yields of benzene or other aromatics, or to produce
in situ catalyst regeneration. Typical operating condi- aviation blending stocks. It also produces large quanti-
tions are: temperature 755–810 K, pressure 10–27 bar, ties of hydrogen that can be used to hydrotreat or
LHSV 1–4 per hour, and H2=HC ratio 3 : 6. The total improve other products. The process features a semi-
capacity of houdriforming units is about 250,000 b=d. regenerative or cyclic configuration and proprietary
catalyst system tailored to the client’s specific needs.
Advantages include cost-competitive installations for
Magnaforming Process
units less than 12,000 b=d, 98 RON products achiev-
able, mild severity operations, and long cycle lengths.
The magnaforming process, which was licensed by
The staged catalyst system has high stability, good
Engelhard Corporation, can be used to upgrade low-
selectivity and selectivity maintenance. It uses the high-
octane naphtha to high-octane reformate. The product
activity catalyst with very high stability and benzene=
is a premium blending component or aromatic hydro-
toluene yields. KX-130 is an excellent debottlenecking
carbon source. The feature that most distinguishes the
catalyst or BTX-producing catalyst. The dual catalyst
magnaforming process from other reforming processes
system offers high-activity catalyst, high benzene=
is its use of a split hydrogen recycle stream to increase
toluene yields, and a C5þ yield advantage. ExxonMobil’s
liquid yields and improve operating performance.
catalyst management techniques for hot flue gas regen-
About half of the recycled gas is compressed and
eration in cyclic units, onstream chlorination, and
recycled to the first two reactors, which are operated
analytical tools for monitoring the catalyst help enhance
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resistance to fouling of the catalyst system increases the highly stable and selective IC-30-type catalyst based
yields of aromatic naphtha product and hydrogen due on modified pentasil zeolite is used in the process.[13]
to the long cycle lengths, which reach 6 mo or more. Because of the acid–base shape-selective mechanism
Optimized operating techniques permit maintenance of the hydrocarbon conversion in the zeoforming
of high catalyst activity throughout each cycle and process, the gasoline product has a lower aromatics
return to fresh activity after each regeneration. content compared to the reformate with the same octane
The increased resistance to fouling also provides for number. Reactions proceeding under zeoforming pro-
expansion of existing plants by using higher space cess conditions allow benzene concentration to decrease
velocities, lower recycle ratios, or increased product below 1 vol% and to produce gasoline with low sulfur
octane. Converted units operate with H2=HC ratios content without naphtha hydrotreating owing to
of 2.5 : 3.5 and long cycles between regeneration. It is insensibility of the catalyst to sulfuric compounds in
believed that a total of 73 rheniformers are onstream the feedstocks. The process is based on the catalytic
with a total capacity of more than 1 million b=d. conversion of linear paraffins and naphthenes into
iso-paraffins and aromatics over zeolite-containing
catalysts, which allows the motor octane number
Ultraforming Process
(MON) of naphtha to increase from 45–60 up to 80–85.
Stepanov et al.[13] reported that a small-scale plant
The Amoco’s ultraforming process (now BP’s) can be
of 120 b=d of naphtha was operated successfully in
used to upgrade low-octane naphthas to high-octane
the north of Siberia, Russia in 1992. Catalyst life
blending stocks and aromatics. The process is a
reached more than 1.5 yr. A new industrial plant based
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and for a variety of feedstocks. The current demand regulations that refiners have been, and will be,
for reforming catalysts is mainly a replacement market required to meet during the coming few years. Table 6
with about 75–80% of it as bimetallics. Reforming presents a compilation of commercial reforming cata-
catalyst vendors continue to develop new catalyst for- lysts that are available by sale or license to refiners.[15]
mulations designed to meet a wide array of challenges. The list provides information on catalyst supplier,
Many of these challenges involve environmental catalyst type, and other selected catalyst properties.