axens 16/1/06 20:38 Page 1

REFINING

Octanizing reformer
options
Staged investment and reformer technology improvement strategies are available for
increasing hydrogen production, cycle time and reliability. Options include revamps
to SR reformers and hybrid SR/CCR Dualformers, as well as new CCR unit investments
Bruno Domergue and Pierre-Yves le Goff Axens
Jay Ross Axens NA

T
he refining industry is investing
heavily in new processing units to
RegenC-2
produce ultra-low-sulphur (ULS) Regenerator Booster
fuels. As a result, hydrogen utilisation is compressor
increasing, on-stream factor and Hydrogen
hydrogen reliability are becoming more Reactors and heaters rich gas
important, and resources for other
investments are scarce. Catalytic
reforming is the preferred technology for
producing high-octane gasoline and is
R-3
R-2

usually the refinerys main source of Recovery

R-1

Separator
hydrogen. Although existing reformers system
in North America are generally not fully
utilised, many are older semi-
regenerative (SR) or cyclic units with
cycle times that are incompatible with
continuous ULS fuels production. They Reformate to
produce less gasoline and hydrogen than stabilisation
newer ultra-low-pressure continuous
catalytic regeneration (CCR) units.
Recycle
CCR reforming Feed
compressor
More than 35 Octanizing and Aromizing
CCR reforming processes for gasoline-
and aromatics-orientated catalytic Figure 1 Axens CCR reforming process
reforming have been licensed world-
wide. Ten new units were licensed in regeneration operations are highly immediate and longer-term savings in
2005. The Axens CCR reforming process automated and require minimal investment, construction and mainte-
is schematically represented in Figure 1, operator attention. nance costs.
including key features for producing The reformers side-by-side reactor The key to unit performance and long
high-octane gasoline or aromatics-rich arrangement, as shown in Figure 1, has catalyst life in CCR reforming is the
petrochemical streams from naphtha. several advantages over the stacked RegenC-2 catalyst regenerator technol-
The catalyst circulation systems of design. Access for construction, ogy. Combined with recently developed
these reformers are designed for long inspection and future modifications to and commercialised catalysts, regener-
and active catalyst service as well as ease the reactors, as well as to the internals, is ators incorporating this technology can
of operation and maintenance. To greatly increased. In addition, thermal provide sustained catalyst performance
ensure low catalyst attrition, the lift expansion problems are minimised and over hundreds of regeneration cycles.
system must be designed for continuous, the reactor structure is lighter and lower Significant technology and monitoring
smooth, non-pulsating and gentle to the ground. This enables an optimal improvements in the coke burn and
lifting. Catalyst is continuously radial reactor design (L/D) without catalyst oxychlorination zones result in
transferred to the regenerator, where the height constraints and a simplified increased catalyst life and improved
coked catalyst undergoes a sequence of internals structure that is less prone to operating flexibility.
steps involving controlled coke mechanical problems due to thermal RegenC-2 consists of four
combustion, oxychlorination and expansion. The reactor placement also independent zones, depicted in the
calcination to restore the catalyst provides for shorter catalyst transfer block flow diagram in Figure 2. These
activity and metals redispersion. The lines, shorter hot transfer lines between zones include:
proprietary RegenC-2 dry burn loop reactors and heaters, plus minimal non- A primary burn zone equipped with
regeneration system is able to perform flowing heel catalyst volume due to the a dry burn loop to minimise moisture
complete catalyst activity restoration use of spherical heads (less than 0.5% of during combustion
under mild conditions to maintain the catalyst inventory compared to A finishing zone with oxygen and
catalyst activity and mechanical many times this in other designs). These temperature control (no sharp
strength. The catalyst circulation and advantages translate into significant exotherms or carbon breakthrough)

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the moisture level in the burn zone.

Spent catalyst Accordingly, a reduction in the moisture
content during combustion lowers the
Dry catalyst dechlorination, which has three
combustion gas Primary advantages:
burn Equipment required for chloride
Air treatment in the combustion effluents is
reduced
Finishing Corrosion potential downstream of
burn the combustion effluent treatment is
Air Dry burn reduced
loop Chloriding agent addition during
oxychlorination to compensate for the
Oxychlorination
Chloriding dechlorination during coke burning is
agent plus water reduced.
Overall, the dry burn loop RegenC-2
Calcination regenerator affords several advantages:
Oxychlorination Extends catalyst life: a significant
calcination gas increase in catalyst life compared to the
hot burn loop (>900 cycles has been
demonstrated)
Regenerated catalyst
Reduces catalyst attrition via
controlled temperature and less severe
Figure 2 RegenC-2 regeneration block flow thermal cycling
Increases catalyst stability through
optimisation of the oxychlorination
operating parameters throughout the
catalyst life
Unit A Unit B Unit C
Base Improves regenerator operation
Unit D Unit E
flexibility due to the separation of the
Relative surface m2/g

burn and oxychlorination gas loops

20 Dry burn loop Reduces downstream corrosion due
to better chloride retention and
Cold burn loop management
40
Discharges of a clean vent gas; ie, no
Hot burn loop chloride-removal equipment is required.
60
CCR catalysts
80 The CR 400/700 and AR 500 catalyst
Number of regenerations series are formulated to meet the specific
needs of gasoline and aromatics
production respectively. They are
Figure 3 Surface area decline vs regeneration cycles in commercial units supplied in either a calcinated or
reduced state.
An oxychlorination zone for metals are the moisture level, temperature and The development of CR 401/AR 501
redispersion combustion time. It is therefore critical follows and anticipates the trend for
A calcination zone to dry the that the water content is kept as low as high-performance ultra-low-pressure
catalyst. possible in the combustion gases. This operation for new or existing units. CR
Coke burning is the principal function observation has led to the incorporation 401/AR 501 have been specifically
of a catalyst regeneration system. It is of a dry burn loop in the RegenC-2 developed for reactor pressures of 3.57
essential that this step be carried out to regenerator to dry the recirculating barg (5090psig), while for higher
completion. However, the coke burning combustion gas. pressures CR 405/AR 505 are preferred.
step is the primary contributor to three The benefits of a dry burn loop are The high-performance low-density
negative factors concerning catalyst shown in Figure 3, where catalyst catalysts CR 701 and 702 are favoured
performance and life: surface area decay (carrier degradation) when reduced catalyst loading is
Metallic phase sintering, which is plotted against a number of regenera- required.
lessens catalyst performance; in tion cycles for the same catalyst in three The combination of catalyst
particular, stability regeneration systems: properties, regenerator design and
Partial dechlorination of the carrier, Hot burn loop: recirculating burning catalyst-transfer systems results in very
which reduces catalytic activity gas is hot and wet low catalyst attrition (<2% of the
Hydrothermal sintering of the Cold burn loop: recirculating gas is inventory per year, or <0.0015% of
carrier, which decreases mechanical washed but not dried circulation). The consequence of
strength and ultimate catalyst life. Dry burn loop: recirculating gas is attrition is greater than the inconve-
The hydrothermal sintering of the washed and dried. nience and expense of catalyst addition.
alumina carrier, which occurs during In normal operation, the metal As fines are produced and build up in
regeneration and, in particular, during dispersion is reconditioned in the the unit, the pressure drop can increase
coke burning, results in a decrease of the oxychlorination zone. The dechlorina- and catalyst circulation problems can
specific surface area of the catalyst. The tion that occurs in the coke burning arise. In some designs, this causes a
leading factors involved in carrier ageing section is predominantly the result of dump and screening of the catalyst on

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P T Q Q1 2006