Catalytic reforming options and

practices
Design and practice in catalytic reforming is evolving to meet refinery challenges,
including lower gasoline pool benzene content and increased demand for hydrogen

Tom Zhou Fluor Enterprises

Frederik Baars Fluor BV

R
efiners throughout the world utilise catalytic line pool component, a C7-C9 cut (IBP-FBP
reforming to produce high-octane reformate 90–160°C) is the preferred choice.1
for gasoline blending and high-value Reformate benzene content can be reduced by
aromatics (benzene, toluene and xylene, BTX) minimising the amount of benzene and benzene
for petrochemical use. Reforming is also a major precursors (cyclohexane and methylcyclopen-
source of refinery-based hydrogen. tane) in the reformer feed via prefractionation.
Reforming operations continue to be chal- Alternatively, the benzene can be reduced by
lenged in the context of lowering gasoline pool post-fractionation of the reformate and further
aromatic/benzene content; however, the cata- processing of the light reformate.
lytic reforming unit is still a mainstay of refinery In a refinery where maximisation of middle
operations. The recent upward trend in hydro­ distillate production is a priority, the heavier
treatment needs has put even more emphasis on portion of the naphtha that is traditionally
reformer hydrogen production. The main differ- routed to a catalytic reformer unit may instead
ences in technology among the various reforming be sent to the kerosene or diesel pool, within
processes are discussed in this article, and flash point specification limits. In most cases, a
special attention is given to chloride control and lighter CRU feed will result in an increased cycle
corrosion management. length for a semi-regenerative (SR) unit due to
decreased coke make.
Feedstock Non-straight-run naphthas (for instance, fluid
The standard feed to a catalytic reforming unit catalytic cracking (FCC) naphtha or visbreaker/
(CRU) is hydro­treated straight-run naphtha coker naphtha) can also be processed in a CRU,
(SRN), typically containing C6 through C11 paraf- but only after severe hydro­treatment involving
fins, naphthenes and aromatics. Naphtha from (di)-olefin saturation, in addition to the basic
different sources varies greatly in its ease of naphtha hydrotreater functionality of removing
reforming. Most naphthenes react rapidly and heterogeneous atoms (sulphur and nitrogen).
efficiently to form aromatics. This is the basic Their higher endpoint and/or higher paraffin
reaction of reforming. Paraffins are the most content results in a higher coke laydown. Cyclic
difficult compounds to convert. A rich naphtha and continuous catalyst regeneration (CCR)
(lower paraffin, higher naphthene content) reformers are generally able to process FCC
makes the operation much easier and more effi- naphtha with a higher feed endpoint as long as
cient. The types of naphtha used as feed to the regenerator capacity exists to burn the additional
CRU can impact the operation of the unit, activ- coke that is produced.2 The reprocessing of FCC
ity of the catalyst and product properties. When naphtha is typically restricted to the lower
catalytic reforming is used mainly for BTX octane middle cut. If desulphurisation only is
production, a C6-C8 cut (initial and final boiling required, processing the FCC naphtha in a selec-
points IBP-FBP 60–140°C), rich in C6, is usually tive hydro­treating unit is the more
employed. For production of a high-octane gaso- straightforward solution.

www.digitalrefining.com/article/1000479 PTQ Q2 2010 1

 operate at a low pressure with
Stacked Combined the associated yield benefits of
reactor feed exchanger higher reformate and hydrogen
Naphtha feed
from treating
Net H2 rich gas yields.
Net gas
CCR compressor Fuel gas
The decision to convert
regenerator high-pressure SR catalytic

Recovery
section
reformers to CCR-type units
Light hinges entirely on economics.5
ends Some reforming licensors have

Separator
developed a hybrid unit, by
Stabiliser
adding a CCR reactor and
regenerator to an original SR
Regenerated
catalyst Fired heaters reforming unit.4,6,7,8 Typical
examples are shown in Figures
Spent Aromatics
catalyst Combined rich reformate
3 and 4. The conversion could
feed cost less than half that of a new
exchanger
CCR and increases throughput
and/or cycle length.4
Figure 1 CCR with stacked reactors Courtesy: UOP To some refiners, a complete
conversion to CCR remains
economically attractive relative
to a hybrid unit, due to the
Regen C–2
regenerator Booster
higher on-stream factor, lower
Hydrogen
compressor
rich gas operating pressure, and higher
Reactors and heaters
yields of hydrogen and naph-
tha.9 Virtually all new
reforming units are of the CCR
design.
Recovery
Separator
R–1

R–2

R–3

system
Reactor design
There are three types of reac-
tors predominantly in use in
Reformate to
stabilisation the reforming process. These
are spherical, downflow and
Feed radial. As catalyst improved
Recycle
compressor over the years, the reactor
pressure could be reduced to
Figure 2 CCR with side-by-side reactors Courtesy: Axens take advantage of the increased
C5+ and hydrogen yields at
Fixed-bed units vs CCR reformers lower operating pressure. At
The conventional CRU type is the SR fixed-bed lower pressure, the pressure drop through the
reforming unit, which is used for limited octane reactor becomes an important consideration;
improvement. The unit is operated at high pres- therefore, more modern designs of reforming
sure to mitigate carbon formation. As carbon units employ reactors that are radial flow in
laydown increases, reactor temperatures are design and combine good flow distribution with
raised to achieve the target octane at the expense low pressure drop.
of reformate yield. A cyclic regenerative process The combined feed is directed from the reactor
with a swing reactor system is used for higher inlet nozzle into so-called scallops, which are
severity and octane operation. With CCR reform- long, vertical channels positioned along the
ing (see Figures 1 and 2)3,4, extremely high entire circumference of the reactor. The scallops
severities are obtainable without frequent shut- have holes or, more commonly these days,
downs due to catalyst deactivation. The units profile wire screens along the entire length,

2 PTQ Q2 2010 www.digitalrefining.com/article/1000479

through which gas passes radi-
ally into the annular catalyst New reactor
bed and inwards to a centre R–4

pipe that collects the reactor Reactors Regenerator

Hydrogen
products and directs them to rich gas
the reactor outlet. Low flow

R–3
should be avoided, as it will

R–2
R–1

Separator
result in accelerated coke
laydown.
Heater Heater Heater New heater
H–1 H–2 H–3 H–4 Air
Reactor metallurgy cooler
Unstabilised
Reactor vessels in a SR CRU reformate
New feed/effluent
service are standalone items exchanger
Recycle
and can be either hot or cold Feed
compressor
shell, depending on design Charge
preference. In cold-shell pump

designs, an internal refractory

lining protects the vessel wall Figure 3 SR and CCR hybrid process Courtesy: Axens
from exposure to the process
temperature. In CCR service,
the reactors are invariably of
the hot-shell design and can be Rx 3 Rx 2 Rx 1
either individually positioned
or stacked to form a compart- Combined
Recontact
system
mented single vessel.8 In a SR feed
exchanger
CRU, a cold wall (carbon steel
with refractory lining) with an

Separator
inner stainless steel liner is the
norm. However, hot-shell Heaters
design necessitates the use of
1.25Cr-0.5Mo, or in some Stabiliser
cases 2.25Cr-1Mo, with stain- section
Rx 4
less steel internals suitable for
Feed
service above 538°C (1000°F) Catalyst
to meet the requirements for regenerator
both high-temperature
strength and resistance to New equipment
hydrogen attack. required

Reforming catalyst and Figure 4 SR and CCR hybrid process Courtesy: UOP
catalyst regeneration
The reforming catalyst consists of noble metals units. The presence of tin (Sn) prevents plati-
impregnated on an alumina base, with a cylin- num agglomeration or sintering during the
drical (SR applications) or spherical shape (SR regeneration and provides better Pt dispersion.2
and CCR applications). A wide variety of metals In the reactors, both the metal(s) and the chlo-
can be used, but platinum is predominantly ride base help catalyse desirable reactions.
used. Multi-metallic catalysts composed of plati- Optimum catalyst performance requires a proper
num (Pt) and rhenium (Re) are the most balance of these two catalytic functions. Catalyst
common type found in a fixed-bed CRU. deactivation usually occurs as a result of coke
Rhenium helps to improve catalyst life by retard- formation covering the active sites of the cata-
ing coke deposition to prevent deactivation. lyst. To regenerate the catalyst, the coke must be
Pt-Sn catalysts are utilised in CCR reforming burned off and the catalyst oxidised (oxychlorin-

www.digitalrefining.com/article/1000479 PTQ Q2 2010 3

 ated to redisperse the platinum and restore the operation is dry during normal operation, this
chloride balance), dried and finally reduced. changes during regeneration, with water being
Each step of the regeneration procedure is criti- formed as a result of coke being burnt off. While
cal to return the catalyst system to its usual high the low chrome reactors are not at risk when hot
performance and to ensure long catalyst life. during regeneration, the area
SR and cyclic reformers utilise fixed-bed downstream at the effluent cooler presents a
reforming reactor(s) for regeneration, while a great risk of corrosion. To maintain corrosion
CCR reformer has a dedicated moving-bed control during regeneration, separator water pH
regenerator with associated piping and equip- is kept above 7 by adjusting caustic injection
ment. In SR operation, the catalyst is allowed to during the coke burning and oxidation steps.
coke up and needs to be regenerated periodically For CCR reforming, the regenerator and its
in-situ. A cyclic reformer has a swing/spare internals are normally made of stainless steel,
reactor to allow unit operating severity to be which is considered to be adequate for chloride
maintained while one reactor is being regener- corrosion resistance, since temperatures inside
ated. A cyclic or CCR reformer is more robust to the regenerator are kept above the water dew
feed upsets, as it is regenerated on-line. The point. However, special attention needs to be
reactor operating pressure is lower than with SR paid to instrument taps and nozzles, where cool-
operation, which is beneficial to reformate/ ing and condensation can occur. Heat tracing
aromatics yield. Although the lower operating and nitrogen purging are required
pressure accelerates coke laydown, this is taken to limit chloride corrosion. Alternatively, the
care of by on-line regeneration. metallurgy can be upgraded from stainless steel
The catalyst regeneration system in a CCR to materials such as Hastelloy.
reformer performs two functions: catalyst regen- Most HCl concentrates in the reformer net gas
eration and catalyst circulation. These days, all and liquefied petroleum gas (LPG). While these
regeneration steps, except for reduction, occur in streams are dry, they do not generally pose
the regenerator. The reduction takes place in the problems inside the CRU, but can create prob-
reduction zone above the first reactor. The cata- lems when mixed with other (wet) streams.
lyst exits the zone and flows by gravity to the Chloride absorbers (on net gas, LPG or stabiliser
first reactor. feed) are typically installed to overcome this.
Catalyst developments continue, with manu- Depending on the CCR regenerator design
facturers constantly introducing catalysts that type, the regenerator vent gas can also contain
exhibit a better yield pattern or a higher activity. significant amounts of HCl. Caustic scrubbers
Reforming catalyst can only be regenerated if are generally employed to remove HCl from the
the cause of the deactivation is sulphur and/or vent gas. Recontacting the vent gas and/or
carbon laydown. Other (permanent) sources of reduction step purge gas with spent catalyst
deactivation will typically require catalyst (aimed at reabsorbing HCl back into the process)
replacement. has recently been introduced11 as a means of
reducing HCl losses and therefore chloride
Chloride-related corrosion control consumption.
To assure the metallic and acidic functions of a
reforming catalyst, chloride is continuously References
injected into the process. Depending on the 1 Prestvik P, Moljord K, Grande K, Holmen A, Catalytic Naphtha
levels of nitrogen in the feed to the CRU, ammo- Reforming, Antos G J, Aitani A M, Marcel Dekker, New York, 2004,
17–18.
nium chloride could form and deposit on process
2 Hydrocarbon Publishing Company, Third Quarter 2009
equipment, with the risk of corrosion or reduced
Hydrocracking and Catalytic Reforming, Worldwide Refinery
efficiency (for instance, in compressors).
Processing Review, 225–273.
Injections with reformate, naphtha or water are 3 UOP, CCR Platforming Process for Motor Fuel Production, www.
an option for cleaning out salts deposited in the uop.com/objects/CCR%20Platforming.pdf.
recycle gas compressor.2 A good design should 4 Domergue B, le Goff P-Y, Ross J, Octanizing reformer options,
focus on removing organic nitrogen from the PTQ, Q1 2006, 67 & 72.
reformer feed and minimising hydrochloric acid 5 1996 ERTC, London, Oct 1996, Global Technology Forum,
(HCl) in the reactor loop. While the SR reformer Surrey, England, 29.

4 PTQ Q2 2010 www.digitalrefining.com/article/1000479

6 Gendler J L, Domergue B, IFP Solutions for Revamping Catalytic the Netherlands, responsible for refinery studies and basic
Reforming Units, 1996 NPRA Annual Meeting, San Antonio, Texas. engineering projects. Email: [email protected]
7 Stephens G, Travers Ph, Mank L, Revamping Catalytic Jun (Tom) Zhou is a Principal Process Engineer with Fluor
Reforming Units, Revue de l’Institut du Pétrole, 1994, 49, 5. Enterprises, Houston, Texas, with experience in front-end and
8 Peters S T, Platforming Technology Advances: CycleX System detailed engineering design for catalytic reforming units. Email:
for Increased Hydrogen Production from a Fixed-bed Reforming [email protected]
Unit, 2003 NPRA Annual Meeting, San Antonio, Texas.
9 1996 NPRA Q&A and Technology Forum: Answer Book, 1996
NPRA Q&A Session, San Antonio, Texas.
Links
10 Brear J M, Williamson J, Integrity and Life Assessment of
Catalytic Reformer Units, www.seseurope.com/htm/SESpapers_ More articles from: Fluor
pdf, SES 2006.
More articles from the following categories:
11 2009 ERTC UOP pre-seminar.
Catalysts & Additives
Fred Baars is a Technical Director with Fluor BV, Haarlem, Reforming

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