IMPROVED HYDROCRACKING

Leading-edge catalysts coupled with outstanding technical service

Criterion Catalysts & Technologies (Criterion) offers a CATALYST SELECTION
broad range of zeolite catalysts to satisfy a variety of We work closely with refiners to select the most appropriate
refinery hydrocracking objectives. We also provide the hydrocracking and pretreatment catalysts to meet their individual
feed pretreatment catalysts that are vital to preserving process needs.
the function of the main cracking catalysts. This involves a detailed analysis in which reference will be made
Hydrocracking is replacing fluidised catalytic cracking as the to feedstock quality; the desired product slate; the design of
refinery conversion process of choice. The reasons are simple: the hydrocracker and its normal operating regime; the amount
the shift from gasoline to diesel in many parts of the world; the of hydrogen available; and the target cycle length. Process
flexibility of the hydrocracking process, which makes it relatively modelling and pilot plant trials are part of the toolbox used to
easy to alter the product slate to meet changing market demands; pinpoint the best catalysts for individual hydrocrackers and also
the ability of the process to make high-quality transport fuels, to develop the most effective unit operating strategy.
particularly ultra-low-sulphur diesel, directly from difficult-to-process
TECHNICAL SERVICE
feeds; and, finally, the ease with which hydrocrackers can be
integrated with ethylene crackers in the petrochemicals sector. Criterion customers benefit from the support of knowledgeable
and experienced technical service engineers at every stage of
The performance of hydrocracking units is fundamentally the process cycle.
dependent on the zeolite catalyst used to break down the heavier
oil molecules. However, as feed quality generally declines, it is The technical support available to customers goes beyond
becoming increasingly common to find units whose performance, advising on the selection of suitable catalysts. We routinely
notably run length, is limited by the decline in activity of the feed provide consultation during catalyst activation and, thereafter,
pretreatment catalyst, the role of which is to protect the zeolite we help customers with information as they seek to optimise
the performance of their hydrocrackers. Using our Cat-Check
from harmful sulphur and nitrogen compounds and trace metals.
knowledge management system, we can help them to build a
clear picture of the way the unit is performing as the process cycle
develops. This helps to customers to optimise operating conditions
to best effect, understand process anomalies and troubleshoot any
Criterion offers a broad range process problems quickly and efficiently. We are always looking
of zeolite catalysts to satisfy a for ways to provide information that will help to increase a unit’s
variety of refinery hydrocracking profit margin.
objectives. We also provide the
pretreatment catalysts that are vital
to preserving the function of the
main cracking catalysts.
To advance the state of the art in hydrocracking catalysis, Criterion
and Zeolyst continue to research techniques to improve zeolite
systems, metal sulphide functions and catalyst shapes, all aimed at
increasing product yields and optimising specific product qualities.

HYDROCRACKER PRETREATMENT 300

Type I catalysts Type II catalysts
Criterion is a global leader in hydrotreating catalysts and has a
track record that stretches back for more than 50 years. Criterion 250

Relative volume activity (%)

catalysts can be currently found in about 850 hydrotreating
units around the world used for product quality upgrading and DN-3620
200
hydrocracker pretreatment.
Over the past 10 years, we have continually pushed the 150 DN-3300
boundaries of hydrotreating catalyst technology and raised
DN-3551
hydrodenitrogenation (HDN) and hydrodesulphurisation (HDS) DN-3100
activity to ever higher levels (Figure 1). Our current hydrotreating 100
offer is based mainly on two technology platforms: ASCENT DN-200
(now in its second generation) and CENTERA. Both of these 50
platforms can be used to formulate CoMo–alumina and NiMo–
alumina catalysts; the former are best suited to low-severity
Figure 1: The activity of Criterion’s leading Type I (DN-3551) and
feed operations and the latter come into their own with more
Type II (DN-3620) hydrocracking pretreatment catalysts compared
challenging feeds, for example, with higher end points, more with earlier generation catalysts.
cracked fractions and higher metal and nitrogen levels.
ASCENT catalysts have a mixture of Type I and II active sites.
They appeal to refiners seeking to strike the best balance PROOF POINT: refinery in the USA
between activity and hydrogen consumption; they are physically
strong, which makes handling straightforward; and they The challenge posed by a refinery operator in the
are easily regenerated (≥90% fresh catalyst activity) using USA was to provide a pretreatment catalyst that would
conventional means. enable feeds containing up to 10% deasphalted oil to
be cracked without reducing its three-year planned cycle
CENTERA catalysts possess 100% Type II active sites and hence
length. We achieved this by using CENTERA DN-3620
offer the highest possible level of activity. They are made using
to increase the HDN activity significantly in the lower part
advanced techniques that result in excellent retention of activity
of the reactor so that the upper level could be loaded
(the active sites are locked into place), which provides refiners
with a larger volume of the less active but more robust
with outstanding operational flexibility.
and highly tolerant ASCENT DN-3551, which essentially
Our most popular catalysts on each of these platforms are created an activity gradient within the reactor and
ASCENT DN-3551 and CENTERA DN-3620. maintained the same HDN activity as before. This system
is enabling the refinery to process 8–10% deasphalted oil
ASCENT DN-3551 for the entire three-year cycle.
A NiMo–alumina catalyst with a good balance of HDN and HDS
activity and a relatively low hydrogen demand. Noted for its stable
high-temperature performance, physical resilience and ease of
conventional regeneration, DN-3551 provides an extremely tolerant,
cost-effective pretreatment solution in many hydrocracking applications.

CENTERA DN-3620
Criterion’s flagship hydrocracker pretreatment catalyst; it has the
highest activity and stability of any of our hydrotreating catalysts. It is
also a NiMo–alumina catalyst but with 100% Type II active sites. It is
the preferred choice in high-severity units running feeds with elevated
nitrogen levels or high percentages of cracked or high-end-point
stocks. The catalyst has class-leading performance and remarkable
retention of activity. Refiners can exploit this last point in different
ways to suit their individual operational objectives: to extend cycle
lengths; to reduce the nitrogen slip to the cracking catalyst; to process
tougher feeds; or, as less reactor volume is taken up by a more active
and stable catalyst, to include additional catalysts in the pretreatment
section with extra functionality.
 ZEOLITE HYDROCRACKING CATALYSTS step-out catalyst being developed to further increase middle
Criterion’s hydrocracking catalysts are made by Zeolyst International distillate yield. State-of-the-art catalyst Z-2623 provides higher
(Zeolyst), a joint venture formed in 1988 with silica and zeolite selectivity than Z-623 with even higher activity and, at the same
specialist PQ Corporation (Figure 2). time, improves the cold flow properties of the middle distillates.

Research conducted by Criterion and Zeolyst has produced a Flexible (FX) series
series of hydrocracking catalysts recognised for their stability and For a flexible portfolio of naphtha and middle distillates, our
good balance of activity and selectivity, which result in long run state-of-the-art catalysts Z-3723 and Z-3733 supersede the
lengths and slow yield declines. Zeolyst catalysts are currently classic 700 series and are specifically designed to convert heavy
installed in more than 70 hydrocracking units around the world. oil feedstocks into high yields of high-quality middle distillates
with lower levels of gaseous by-products. Z-2723 provides the
High diesel (HD) series same high activity as Z-3723 with even higher middle distillate
Designed for maximum diesel yield, our classic 500 series selectivity while improving cold flow properties. Step-out catalyst
includes Z-503, which has been used widely in combination with Z-FX10 maintains the high middle distillate yield of Z-2723
HDN catalysts in hydrocracker pretreatment units to convert the while improving the quality of the hydrowax normally sent to an
most difficult nitrogen compounds more easily. Our step-out HD ethylene cracker. Its advanced formulation enhances aromatics
catalyst range is specifically designed to maximise the production saturation and thus improves middle distillate yield, product
of heavier distillates from more difficult feedstocks. This includes quality and catalyst stability. This combination of properties
Z-HD10, which is designed for even higher diesel yield in second- makes the catalyst especially suitable for converting high-boiling-
stage reactors, and Z-HD11, which improves the properties of the range feedstocks into high-quality diesel and jet fuel products in
unconverted oil products. State-of-the-art catalyst Z-2513 provides either recycle or once-through operations.
the same high diesel yield with even higher activity and, at the
same time, improves the cold flow properties of the diesel. Naphtha (NP) series
Designed for maximum naphtha yield, our classic 800 series
Middle distillate (MD) series catalyst range includes Z-853, which is specifically designed
Intended for use in maximum middle distillate (kerosene and to hydrocrack heavy oil feedstocks to produce high yields of
diesel) applications, our classic 600 series includes Z-623 high-quality naphtha and middle distillates in either recycle or
and Z-673, which combine intermediate activity with high once-through operations. Step-out catalyst Z-NP10 provides even
selectivity to middle distillates. These catalysts are specifically more heavy naphtha product with reduced liquefied petroleum
designed to provide a constant high yield of kerosene and gas yield.
diesel with excellent product properties. They are also tolerant
of the relatively unreactive molecules in recycled unconverted oil
streams, as they require only low bleed rates to prevent longer-
term deactivation and polyaromatic deposition. Z-MD10 is a

Middle distillate/ Figure 2: Middle distillate selectivity

Diesel Middle distillate naphtha Naphtha
(150–370°C) as function of activity at equal
conversion in a series-flow application.
Z-2513
Z-503
Z-513
Middle distillate selectivity

Z-2623
Z-603

Z-623 Z-2723
Z-FX10
Z-673
Z-3723
Z-723 Z-3733
Z-733 Z-NP10
Z-803 Z-853
Z-863
Z-753

Activity
Classic State of the art New step out
 PROOF POINT: Shell Deer Park Refining PROOF POINT: North American refiner

Shell Deer Park Refining increased its profits by tens A North American refiner replaced Z-853 with Z-NP10
of millions of dollars after collaborating with Criterion, in a series-flow hydrocracker. This was on the basis of
Zeolyst and Shell Global Solutions on a hydrocracker the new catalyst’s relatively low production of C4- light
revamp. A new catalyst system, new reactor internals ends. The refiner’s usual feedstock is 100% fluidised
and a revised operating strategy improved the catalytic cracker cycle oil. In naphtha mode, the unit
flexibility of the hydrocracker, thereby enabling it to achieves up to 95% conversion based on a 204°C
swing between gasoline and distillate modes to take cut point. In kerosene/diesel mode, it achieves up to
advantage of seasonal product demand shifts. 70 vol% production of middle distillates based on a
177°C cut point.

PROOF POINT: A refinery operator in TECHNOLOGY LEADERSHIP

the Netherlands

A refinery operator in the Netherlands was finding it Criterion Catalysts & Technologies is an integral part of
very difficult to make its 19-month hydrocracker cycle the Shell Global Solutions network of companies. This
target owing to loss of pretreatment catalyst activity, gives us a deep insight into industry needs and trends,
which was the result of deteriorating feed quality. and a strong feel for the business from the viewpoint of
At Criterion’s suggestion, the operator switched to a major refinery owner and operator.
CENTERA DN-3620. Once the unit had stabilised, the
We also gain access to process modelling and
weighted average bed temperature data indicated that
optimisation technology targeted at refining
a 19-month cycle length would be easily achieved.
applications, which is particularly valuable when it
On this basis, the operator decided to use the
comes to more fundamental catalyst studies.
activity advantage to feed the unit with an increased
proportion of heavier vacuum gas oil from the vacuum Most importantly, our strong links with Shell Global
distillation unit. Solutions, a leading refinery technology licensor,
facilitate genuinely integrated and customised
hydrocracking solutions encompassing process design,
PROOF POINT: Canadian hydrocracker reactor internals and catalysts, all three elements being
used to process synthetic feed of the same high standard.

The run length of a Canadian hydrocracker used to • Shell Global Solutions provides technical support to
process synthetic feed was limited by the performance over 50 refinery sites worldwide.
of the pretreatment catalyst. Pilot plant trials indicated • It has signed 12 hydrocracking licences in the last five
that CENTERA DN-3620 would provide a 5°C increase years.
in activity under the conditions in the unit. This was • It has more than 60% of the hydroprocessing reactor
subsequently confirmed in the refinery hydrocracker, which internals market.
is no longer limited by the performance of the pretreatment • Shell is one of the largest hydrocracker operators in the
catalyst. The operator is using the improved activity to world, with its capacity of 512,000 bbl/d.
achieve a lower nitrogen slip to the cracking reactor to
preserve the activity of the cracking catalyst and so extend
the cycle length.

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.