Chemical Engineering January 2022 - 23

Haldor Topsoe
WINNING ACHIEVEMENT
Haldor Topsoe:
TK-6001 HySwell™ catalyst
Today, petroleum refiners globally
must comply with ultra-low sulfur
fuel legislation, and for commercial
reasons, they aim to maximize production
of gasoline, jet and diesel
fuels. This results in tremendous demand
for absolute top-tier nickel and
molybdenum-based catalyst (NiMo)
for ultra-low sulfur diesel (ULSD) or
hydrocracker pretreat reactors.
Another driver is the availability of
low-cost hydrogen. When catalytically
added to middle distillate fractions,
hydrogen increases the liquid
volume swell and produces higher
volumetric yields of valuable products.
Consequently, a catalyst that
maximizes hydrogen uptake into hydrocarbon
streams becomes desirable.
Particularly, a NiMo catalyst has
high activity for such a mechanism.
Petroleum refiners need catalysts
with the highest possible activity. Despite
the tremendous improvements
in catalyst technology over the past
20-30 years, refiners are still looking
for the absolute best NiMo catalyst
for their ULSD or hydrocracker pretreat
reactors.
So far, only unsupported catalysts
have had the required activity. However,
unsupported catalysts are very
costly and cannot be regenerated.
With these factors in mind, Topsoe
decided to develop an alumina-supported
catalyst to deliver the required
activity - the HySwell catalyst family.
Specifically, alumina-based hydrotreating
catalysts will help minimize
the operating cost when targeting
volume swell. Furthermore,
HySwell catalysts can be regenerated,
and they utilize the active metals
better, which drives down cost
compared to bulk-metal catalyst
formulations.
This
is
sustainable. A target
clearly more
activity
improvement
compared to standard
catalysts was set to 5-7°C, which is
equal to 15-20%.
How it was done. By employing
advanced microscopy, Topsoe researchers
discovered how unique
catalyst preparation techniques influence
catalytic
functions
at
the
atomic
scale. This led to the development
of an improved alumina
structure and optimization
of the interaction between
the active metals and
the alumina support. As a
result, Topsoe devised very
active and stable CoMo/NiMo
catalyst formulations.
pore
The HySwell technology
exploits this combination of
higher concentration of active
metals and optimized interaction
to the highest degree yet.
This unique technology combines
the earlier BRIM and HyBRIM
technologies with a new
proprietary catalyst preparation step.
As a result, it substantially increases
the activity of both direct desulfurization/denitrogenation
and hydrogenation
sites without compromising
catalyst stability.
In 1984, Topsoe's pioneering reFIGURE
1. Shown here is the winning team from Haldor Topsoe:
Anders Bo Jensen, product line director; Lars Pilsgaard Hansen,
principal scientist; Per Zeuthen, senior director; Magnus Magnussen,
principal scientist; Frank Bartnik Johansson, R&D director
searchers, led by Dr. Henrik Topsøe,
published results showing that there
was a modified Co-Mo-S structure
with substantially higher activity per
active site than traditional Co-Mo-S
structures. The two structures were
called Type I and Type II sites.
In the early 2000s, Topsoe's commitment
to fundamental research in
surface science paid off again, and
a new activity site was discovered:
the BRIM site. Using scanning tunneling
electron microscopy (STM),
researchers visualized these new
activity sites and have been able to
elucidate the catalytic mechanisms
taking place.
The BRIM sites are located close
to the edges on top of the Co-MoS
(or Ni-Mo-S) slab structures. Here,
the BRIM sites act, being metallic in
nature, with the pi-electron clouds of
the organo-sulfur reactants. This interaction
draws the most difficult sulfur
molecules in for the initial hydrogenation
step, enhancing their ability
to further interact with the nearby
Type II sulfur vacancies.
Topsoe's HyBRIM technology was
commercialized in 2013. It includes
an improved production technique
in which the BRIM technology is
combined with a proprietary catalyst
preparation step. This technique
ensures better dispersion of active
components on the surface of the
support along with optimized metalsupport
interactions. Together, they
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facilitate both the formation of more
active Type II sites and promote
higher dispersion of the molybdenum
slabs of Mo/Ni (Mo/Co).
Yet another step increase in activity
is obtained through HySwell,
which involves an improved production
technique for NiMo hydrotreating
catalysts. It combines the BRIM
and HyBRIM technologies with a
proprietary catalyst preparation step.
Merging previous technologies with
novel atomic-level insights enabled
Topsoe to design a metal slab structure
characterized by an optimal interaction
between the active metal
structures of even higher concentrations
and the catalyst carrier. The activity
of the Type II sites is positively
influenced by the improved metalsupport
interaction.
HySwell technology exploits this
combination of a much higher concentration
of active metals and, in
turn, a better Ni promotion of the
sulfided molybdenum slabs through
the optimized interaction. Thus, the
activity of both direct desulfurization/
denitrogenation and hydrogenation
sites are substantially increased,
without compromising catalyst stability.
Ultimately, this increases both
the hydrodesulfurization (HDS) and
hydrodenitrogenation (HDN) performance
of the catalyst.
Commercial production. During
the catalyst development, and prior
to the production at commercial
scale, all the experimental catalysts
have been tested and evaluated by
use of advanced pilot plants, and
products have been analyzed using
cutting-edge analytical tools. After
developing a successful and stable
catalyst recipe, it was decided to
23
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Chemical Engineering January 2022

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