Naptha Hydrotreating Catalysts PDF

Naphtha hydrotreating CATALYSTS
Dealing with the more challenging streams

Criterion is a world-leading supplier of naphtha hydrotreating
catalysts, the key to the effective removal of sulphur and nitrogen
compounds from this valuable refinery stream. We supply about
one-third by weight of all the naphtha hydrotreating catalyst
purchased globally and about two-thirds of all the catalyst used
by refiners operating higher-severity units.
Criterion works with customers to select the most appropriate
catalysts and reactor loading strategies based on naphtha
composition, the design of the individual process unit and the
prevailing operating conditions and constraints. Years of research
and development in this area combined with extensive commercial
experience mean we have the capacity to devise catalyst solutions
for even the most challenging naphtha hydrotreating applications.
Performance and reliability

Naphtha is catalytically reformed within many refineries
to produce a high-octane gasoline blending component.
Catalytic reforming is also a very important refinery process
for another reason: the reformer is a significant source of
the hydrogen required by various critical processes across
the refinery and often in short supply. The performance
and reliability of the reformer are heavily dependent on
the quality of the naphtha feedstock. Sulphur and nitrogen
compounds must be removed from the naphtha to protect
the sensitive noble metal catalysts (usually platinum but also
rhenium) used in the reforming process.
Industry benchmark catalysts

Criterion catalyst DN-200 was launched in the late 1990s
and remains the naphtha hydrotreating catalyst of choice for
many refiners. Specified by more than 100 different customers
worldwide DN-200 is a NiMo alumina catalyst with excellent
stability, which is essential for treating more challenging naphtha
streams. It offers outstanding hydrodenitrogenation (HDN) and
olefin saturation activity; its hydrodesulphurisation (HDS) activity
is also very close to that of equivalent Criterion CoMo catalysts.
The optimised pore size distribution and promoter composition
prolong the life of the catalyst when treating either straight-run or
cracked naphthas. Good results have been obtained with DN200, even at relatively low hydrogen partial pressures.
DN-3531 catalyst was introduced in 2006 and is an alternative
to DN-200. This catalyst is also a NiMo alumina, but it is based
on Criterions industry-leading ASCENT technology platform.
An advanced alumina support, improved metals impregnation
and greater dispersion of the active sites translate into superior
activity, which can be used to raise throughput, process heavier
feeds, extend cycle lengths or achieve target sulphur and nitrogen
specifications at lower hydrogen partial pressures. DN-3531 is
the ideal choice for tougher feeds, such as cracked and coker
naphthas or naphtha derived from tar sands, which call for
maximum HDN activity.
Both DN-200 and DN-3531 have excellent track records and
can be supplied in the oxidic or presulphided form.
Nitrogen removal is the key

The real strength of our catalysts for this application is
nitrogen removal. Getting rid of nitrogen prevents the
formation of ammonium chloride in the downstream section
of the catalytic reformer and protects the chloride balance
in the unit. This is important because, although the noble
metal provides the catalytic sites for the dehydrogenation
reactions occurring in the reformer, it is the chlorinated
alumina support that has the acid sites to promote
isomerisation and ring closure.
Dealing with the tougher

challenges
Throughput and cycle lengths in naphtha hydrotreaters, especially
those running tougher feeds, are less likely to be limited by loss
of catalyst activity than by the excessive pressure drop caused by
fouling of the catalyst bed. This is the generally the result of the
oxidative polymerisation of the reactive olefinic species in cracked or
coker naphthas to produce gums, which ultimately convert to coke.
To defeat this problem Criterion has developed the SENTRY OptiTrap
product portfolio: top bed catalysts and active and inert supports
with various physical structures, void levels and flow properties.
Using OptiTrap materials, we can design a top-bed grading system
to filter and evenly distribute foulants rather than having them build up
on the main hydrotreating catalyst, consequently blocking the flow
through the reactor and increasing the pressure drop.
Hydrotreating coker naphtha often presents another specific
challenge: dealing with the silicon oils that this material often
contains. These originate from the polydimethylsiloxane generally
added to the delayed coking process to suppress foaming. Under
the conditions in most naphtha hydrotreaters, the silicon oils transform
to silica gels that absorb onto the catalyst surface and restrict access
to the active sites, thereby leading to premature deactivation.
Whereas the average cycle length of a naphtha hydrotreater might
be three or more years, coker naphtha hydrotreaters can be limited
to 12 months if this issue is not addressed.
Criterions answer to this challenge is SENTRY MaxTrap[Si],
an alumina-based catalyst with moderate HDN activity and
a structure designed to accommodate unusually high levels
of silicon. It is typically used in stacked catalyst systems in
combination with higher-activity hydrotreating catalysts.
PROOF POINTS
Liaohe Petrochemical, China
One of Liaohe Petrochemicals aims in revamping its
coker naphtha hydrotreater (a twin-reactor unit) was to
expand its capacity from 150,000 t/y to 200,000 t/y.
The trouble was that the unit was prone to pressure drop
caused by coking, which meant frequent shutdowns to
skim the top off the catalyst bed. Criterion helped the
operator by formulating a catalyst solution based on
DN-200 as the main hydrotreating catalyst and protected
from coking by a carefully designed guard bed for the
upper part of the first reactor. This comprised a series of
OptiTrap grading materials and catalysts of decreasing
particle size and increasing activity.
The unit has performed well since its restart at increased
throughput. The guard bed has proved effective in
combating the pressure drop issue, and the HDN, HDS
and olefin saturation levels have all met the refiners
expectations, despite maintaining a relatively low
operating temperature. Liaohe Petrochemical expects to
make its target cycle length for the unit.
Flexicoker operator, USA

A US refiner sought to extend the cycle length of its
naphtha hydrotreating unit, which was running a blend
of straight-run naphtha with the product of its flexicoker
unit. The challenge was to deal with the silicon entering
the unit with the coker naphtha stream. Criterion worked
with the refiner to develop a sophisticated catalyst loading
strategy aimed at maximum activity combined with strong
silicon resistance. The unit was operated with a guardbed reactor and this was loaded with OptiTrap grading
materials and DN-200 for efficient olefin saturation. The
twin main reactors were loaded with 45% MaxTrap[Si],
20% DN-140 (a moderately active hydrotreating catalyst
with good silicon tolerance) and 35% DN-3531, the latter
to provide the bulk of the required HDN and HDS activity.
Although, for other reasons, the unit was shut down
following its planned 12-month cycle, the results from
a hot-loop silicon sampling system installed in the unit
indicated that the run could have been extended for up to
five months, such was the improved state of activity of the
catalyst as a result of the new loading strategy.
CONTACT US
For more information about how we can help you to enhance operational performance, meet increasingly stringent environmental
regulations and increase revenues, visit us at www.criterioncatalysts.com.
Criterion Catalysts & Technologies LP is a wholly owned affiliate of CRI/Criterion Inc. It supplies total packages of catalysts, services and solutions for refineries and is a leading provider of
hydroprocessing, reforming, and specialty catalysts.
Criterion Catalysts & Technologies LP (CRITERION) is a wholly owned affiliate of CRI/Criterion Inc. and an affiliate of the Shell Global Solutions network of companies.
CRITERION and its affiliates are dedicated to providing a broad customer base with effective and cost-efficient catalysts and technologies available in focus areas that include the entire range of
hydroprocessing applications.
The information contained in this material is intended to be general in nature and must not be relied on as specific advice in connection with any decisions you may make. CRITERION is not liable
for any action you may take as a result of you relying on such material or for any loss or damage suffered by you as a result of you taking this action. Furthermore, these materials do not in any way
constitute an offer to provide specific products or services. Some products or services may not be available in certain countries or political subdivisions thereof.

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Naphtha hydrotreating CATALYSTS

Dealing with the more challenging streams

Performance and reliability

Industry benchmark catalysts

Nitrogen removal is the key

Dealing with the tougher

Flexicoker operator, USA

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