Hydrotreating catalyst

White paper

DEVELOPMENTS
IN HYDROTREATING
CATALYST
How a second generation hydrotreating catalyst was developed for high
pressure ultra-low sulphur diesel units and hydrocracker pretreaters

Prepared by:
Michael Schmidt
Topsoe A/S, Copenhagen, Denmark
CONTENTS

1. INTRODUCTION 3

2. CONTINUOUSLY IMPROVING ALUMINA BASED CATALYSTS 4

3. CONCLUSION 9

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1.
INTRODUCTION

The worldwide market demand for more active NiMo The dramatic drop in natural gas prices observed
hydrotreating catalysts is extraordinary. Despite particularly in the US has resulted in a low production
tremendous improvements in catalyst technology for cost for hydrogen. The low cost of hydrogen makes it
the past 20-30 years, ultra-low sulphur fuel legislation very profitable to add hydrogen catalytically to middle
and the shift towards VGO hydrocracking to maximise distillate fractions, thereby increasing the liquid volume
diesel production are more than ever forcing refiners to swell, resulting in higher yields of valuable diesel.
search for the absolute top tier NiMo catalyst for their
ultra-low sulphur diesel (ULSD) or hydrocracker pretreat To address these requirements, refineries continuously
reactor. need better, yet cost-efficient, alumina based catalysts
with the highest possible activity in order to obtain
the desired boost in performance and hydrogen
consumption. Furthermore, alumina based hydrotreating
catalysts will help minimise the operating cost when
targeting volume swell in comparison with higher cost
unsupported catalyst formulations.

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2.
CONTINUOUSLY IMPROVING
ALUMINA BASED CATALYSTS
Topsoe has been at the forefront of important Topsoe’s NiMo catalysts that are developed today
technological breakthroughs in the hydroprocessing are around three times more active than the
industry for decades and continuously explores the catalysts produced in the 1990s. Figure 1 illustrates
possibilities within this area. In the 1970s, Topsoe the development of the company’s many catalyst
discovered the active CoMoS phase in hydrotreating generations. Since Topsoe’s scientists employed tools
catalyst, which revolutionised the catalyst world such as electron microscopes, in situ monitoring,
by applying fundamental research in the catalyst and high throughput screening in their research
development approach. In the 1980s, Topsoe programmes, we have made considerable progress
researchers, headed by Dr Henrik Topsøe, discovered within hydrotreating and hydrocracking catalyst
the difference between Type I and Type II hydrotreating development. The BRIM and HyBRIM catalyst
catalysts and gave them the names that are known technologies are the direct outcomes of this scientific
throughout the industry today. With this breakthrough, approach.
the hydroprocessing catalyst development entered
the nanotechnology era, and the Type II hydrotreating HyBRIM technology was originally introduced with
catalysts became the industry standard for high- Topsoe’s TK-609 HyBRIM in 2013 and has since been
activity catalysts. In the early 2000s, Topsoe’s research extended to include several different hydrotreating
in surface science paid off again, and a new activity site catalysts covering medium to high pressure refinery
was discovered: the BRIM site. With this finding, Topsoe applications. As mentioned above, the need for ULSD
developed BRIM technology within both the CoMo and production from low quality crudes and higher severity
NiMo type catalysts, which fuelled Topsoe’s unparalleled hydrocracking is creating a need for even better
growth in market share globally due to a top tier catalyst catalysts.
portfolio.
During the past three years, HyBRIM technology has
From BRIM to HyBRIM been broadly recognised by the industry to be at the
Topsoe’s latest catalyst technology, HyBRlM, involves forefront of what is possible within hydrotreating. In
an improved production technique for both NiMo and addition, more than 100 hydrotreating units around
CoNiMo hydrotreating catalysts. It combines the BRlM the globe have a HyBRIM catalyst installed right now.
technology with a proprietary catalyst preparation step. However, Topsoe’s researchers recently discovered even
The synergistic effect of merging the two technologies more potential within the HyBRIM method – a potential
has enabled Topsoe to design an advanced metal slab utilising the active metals to an even higher extent and
structure that is characterised by an optimal sites is securing a dispersion of active sites to a level never
positively influenced to a high degree by this interaction seen before. Therefore, Topsoe is launching the second
between the metal slab and the carrier. HyBRIM generation of HyBRIM technology – the TK-611 HyBRIM
technology exploits this interaction and substantially catalyst with 25% higher activity for both sulphur and
increases the activity of both the direct sites and the nitrogen removal.
hydrogenation sites without compromising the catalyst
stability.

FIGURE 1: Topsoe’s catalyst development progress – from Type I through second generation HyBRIM.

Hydrotreating catalyst TO CONTENTS 4

Higher activity, same stability Refiners also benefit from purchasing more opportunity
When applying the TK-611 HyBRIM catalyst in either crudes or processing more LCO and they will have a
ULSD or hydrocracker pretreatment service, the stronger and robust catalyst candidate to handle these
improved activity can be exploited in several ways. more challenging feedstocks. In any case, TK-611
Obviously, a higher activity is often used to operate HyBRIM will significantly improve the profitability of
the unit as in previous cycles, only at a lower reactor refinery assets. Figure 3 shows ULSD pilot plant
temperature, which then yields longer cycle lengths. testing and compares TK-611 HyBRIM with TK-609
However, the new high activity can also be utilised in HyBRIM side-by-side. It is seen that if the two catalysts
terms of increasing unit throughput or, in the case are operated at exactly the same conditions and at
of a hydrocracker, to lower the nitrogen slip from the a reactor temperature giving 10 wt ppm product
pretreat section to the cracking section, resulting in sulphur for TK-611 HyBRIM, then TK-609 HyBRIM
higher conversion and better yields. In addition, TK-611 will simultaneously deliver a product with 32 wt ppm
HyBRIM will increase the volume swell due to better sulphur. Hence the activity advantage of TK-611
hydrogenation functionality. HyBRIM corresponds to a delta product sulphur of
22 wt ppm at ULSD conditions, which is a remarkable
step-change in activity.

The same type of experiment is illustrated in Figure 4

for vacuum gas oil (VGO) at hydrocracker pretreatment
conditions. While 62 wt ppm product nitrogen slip is
achieved with TK-609 HyBRIM, TK-611 HyBRIM, at exactly
the same conditions, is able to deliver a product nitrogen
slip of only 26 wt ppm. Such a difference is a substantial
improvement for a hydrocracker pretreating unit.

Image of TK-611 HyBRIM

FIGURE 3 Comparing TK-611 HyBRIM with TK-609 FIGURE 4. Data for hydrocracker pretreatment
HyBRIM in ultra-low sulphur diesel service. service for TK-611 HyBRIM versus TK-609 HyBRIM.

%S

/API

Hydrotreating catalyst TO CONTENTS 5

High start-of-run activity is obviously important; More volume swell
however, activity has no real meaning unless it is Introducing as much hydrogen into the distillate fractions
accompanied by high catalytic stability, ensuring that as possible can, as previously mentioned, be very profitable
improved performance is maintained over the when excess hydrogen is available. The term ‘volume swell’
projected cycle. Some catalyst formulations on the refers to the increase in the liquid volume when the product
market display an impressive fresh activity; however, density and distillation are lowered by hydrotreating. This
due to the nature of these catalysts, there is an initial includes contributions from removing sulphur, nitrogen (only
line-out deactivation caused by the nitrogen species a very small contribution), and hydrogenation of olefins.
present in the feed passivating the most active sites. However, the main contributor is without doubt the saturation
When these types of catalysts are installed, they will of poly-, di-, and mono-aromatics.
typically have lost their activity benefits after four to
six weeks on-stream. Topsoe has previously demonstrated that there is a
strong correlation between the observed density
During the development of BRIM and subsequent improvement and the degree of aromatic saturation
HyBRIM technologies, Topsoe has successfully been (%HDA). Aromatics saturation is controlled by the catalyst’s
able to modify the alumina structure and catalytic hydrogenation activity, the presence of inhibitors,
surface. By employing scanning electron microscopy such as nitrogen species, and by thermodynamic
(SEM) and transmission electron microscopy (TEM) equilibrium. The overall amount of hydrogen consumed by
techniques, Topsoe’s researchers have observed how hydrodearomatisation (HDA) reactions is of course also
the catalyst preparation steps influence the catalyst dependent on the actual amount of aromatics present in
functions. This knowledge has led to an improved the feed (see Figure 6). A simple way to quantify the volume
alumina pore structure and an optimised interaction swell is to compare the liquid product density with the feed
with the alumina support, providing very active and density. This is an easy approach and is based on available
stable CoMoS/NiMoS catalyst formulations. The data data; however, it does not take the yield losses into account.
shown in Figure 5 compares the stability of the new The correct way is therefore to compare the increase in
TK-611 HyBRIM with TK-609 HyBRIM in VGO the C5+ volume yield with the fresh feed. This method is
hydrocracker pretreat service at the same operating accurate; however, these data are not always readily available
conditions. The testing reveals that even though TK-611 from commercial units or from simple pilot tests, as it requires
HyBRIM is operated at higher sulphur and nitrogen fractionation and the ability to close the mass balance.
conversion levels, due to its higher activity, the two
catalysts exhibit exactly the same performance stability.

FIGURE 5. Catalyst stability for TK-611 HyBRIM versus FIGURE 6. Obtained volume swell with HyBRIM catalyst
TK-609 HyBRIM in hydrocracking pretreat service. in a LCO hydrocracker.

Run time, h

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Topsoe’s researchers have previously published that the swell observed with Feed B corresponds to gaining
presence of nitrogen and, in particular, basic nitrogen more than 3300 b/d of additional liquid out of a 40
compounds strongly inhibits HDA reactions. Therefore it 000 b/d unit. This is remarkably high in conventional
is beneficial to remove nitrogen to very low levels, lower hydrotreating without any cracking catalyst and is
than 2–3 wt ppm N, in order to increase HDA and the the result of a high degree of aromatic saturation.
associated volume swell. Consequently, TK-611 HyBRIM This volume swell represents an additional profit of
with maximum activity for nitrogen removal (HDN) will about $40 million per year even after subtracting the
also provide the highest volume swell. cost of the extra hydrogen that is consumed in the
hydrotreater. The value is based on an oil price of $45/
Figure 6 illustrates the effect on volume swell when bbl, and profitability will obviously increase with the
changing the operating conditions and feed blend. increasing cost of crude oil As part of the data shown
The pilot plant test was conducted simulating a LCO in Figure 3, we also obtained volume swell data for
hydrocracker pretreat unit using a HyBRIM catalyst the two catalysts, enabling a direct comparison of the
as the main treating catalyst. It included five different hydrogenation and hydrodearomatisation difference
conditions, where pressure, temperature, space between first and second generation HyBRIM catalysts
velocity, and LCO amount in the feed blend were at the same reactor conditions. In Figure 8, the
varied. The results show that the HyBRIM catalyst difference in volume swell based on density reduction
removed the nitrogen to very low levels, below 0.2 wt is depicted. Despite a quite low feed aromatic content,
ppm N, which is the detection limit. Consequently, this TK-611 HyBRIM delivers 20% higher volume swell
indicates that saturation of aromatics and, in particular, compared to TK-609 HyBRIM at ULSD conditions.
monoaromatics should take place in the last part of the This is a significant difference, and the improvement is
reactor. In this pilot plant test, the temperature has been remarkable because TK-609 HyBRIM is already a high
kept in the low range in order to avoid thermal cracking. volume swell catalyst.
As expected, Feed B, being very rich in aromatics due
to the high LCO content, obtained the highest volume Figure 9 reveals the main reason for the 20% higher
swells at test conditions 2, 3, and 4. volume swell. At ULSD conditions, the product
nitrogen for both catalysts is low and actually below
In Figure 7, the corresponding aromatics content from the detection limit. This means that the ‘mono- aro-
Feed B is plotted. It is seen that test condition 3, where matics saturation high-way’ is fully open with the
the highest volume swell is reached, is also where the nitrogen inhibitors removed. At such conditions, the
most aromatics are saturated. This can be explained by hydrogenation potential of the catalyst is providing the
the higher reactor temperature and low space velocity. volume swell, and it is therefore observed that TK-611
Monoaromatics especially are saturated the most at HyBRIM is saturating 18% more monoaromatics than
condition 3, and there is actually a correlation between TK-609 HyBRIM.
the obtained volume swell and the residual content of
monoaromatics. In refinery terms, the highest volume

FIGURE 7. Aromatics content in feed and products in Feed B case.

Feed B
Feed B condition 2
Feed B condition 3
Feed B condition 4

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FIGURE 8. Volume swell comparison of TK-611 HyBRIM versus TK-609 HyBRIM at ULSD conditions.

FIGURE 9. Aromatics content before and after ULSD hydrotreating with TK-611 HyBRIM and TK-609 HyBRIM.

VGO feed
SG 0.864 Pressure 70 barg (1015 psi)
S 0.62 wt% SV 1.0/h
N 696 wt ppm

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3.
CONCLUSION

The second generation of HyBRIM technology is

now available with the introduction of TK-611 HyBRIM
catalyst. The 25% higher activity of TK-611 HyBRIM
compared to first generation TK-609 HyBRIM catalyst
unlocks additional flexibility to obtain longer catalyst
cycles, more throughput, better product qualities
or even processing of more severe feedstocks. The
activity boost can be translated into lowering the
reactor temperature significantly in hydrocracker
pretreating and ULSD units, while simultaneously
obtaining the same conversion of sulphur and
nitrogen. Equally important, it is established that
second generation HyBRIM technology exhibits
the same high stability that refiners have come to
expect from the BRIM and HyBRIM catalyst series. It
has been demonstrated that TK-611 HyBRIM catalyst
has significantly higher hydrogenation activity than
TK-609 HyBRIM catalyst due to its higher activity
for nitrogen removal, an ability that will provide
higher volume swells at similar conditions, resulting
in substantially increased profitability for the
refinery asset. In conclusion, the advantages of the
new TK-611 HyBRIM can be utilised to improve the
overall profitability and economy of all hydrocracker
preteating and ULSD in multiple ways.

HyBRIM and BRIM are trademarks of Topsoe

www.digitalrefining.com/article/1001284

Hydrotreating catalyst TO CONTENTS 9

Founded in 1940, Topsoe is a global leader in
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