New catalysts for low and medium

pressure hydrotreating
A catalyst platform provides higher performance in middle distillate hydrotreating
applications with limited hydrogen, difficult feedstocks and severe operating conditions

Andrea Battiston, Adel Abdo, Luca Moraca, Leon Van Den Oetelaar, Edwin Van Rooijen, Henk Jan
Tromp, Jelle Van De Vall and Eelco Vogt
Albemarle Catalysts; Utrecht University

I
n recent years, new and
improved hydrotreating cat- 14 000 140
alysts have been introduced Tons
to the market primarily to serve 12 000 Applications 120

Applications (MD+FCC-PT)
Sales, tons (MD+FCC-PT)

operations with high pressure 10 000 100

and hydrogen availability. On
80
the other hand, catalyst inno- 8000

vation for operations limited 6000 60

by hydrogen, such as low and
4000 40
medium pressure middle distil-
lates-hydrotreating (MD-HT), 2000 20
has been slower. The challenge
0 0
is to be able to deliver both pre- 2015 2016 2017 2018 Total
mium activity and stability in
applications with limited hydro- Figure 1 KF 780 catalyst in FCC-PT and middle distillate hydrotreating units
gen, difficult feedstocks and combined
severe operating conditions in
general. KF 780 was introduced to the market at the
To improve stability for hydrogen constrained beginning of 2015, first of all for FCC-PT appli-
MD-HT operations, suppliers followed a defen- cations. Its main operational targets in FCC-PT
sive approach and sought to develop moder- are to maintain a low sulphur product level via
ately active catalyst systems with low selectivity improved HDS and to reduce nitrogen and aro-
for nitrogen removal. The drawback in adopt- matics levels for better yields and operations in
ing such catalysts is that, while benefiting from FCC units. After proving itself in this demanding
their stability in operation, refiners are still not service, it was rolled out to the ultra low sulphur
able to maximise activity and thereby extract diesel (ULSD) segment.
full operating potential and profit from their The acceptance of KF 780 by refiners for both
critical units. applications has been positive, with more than
Albemarle responded to the need for low 12 000 tonnes delivered and 130 operations
and medium pressure, higher performance served worldwide since 2015. An overview of
catalysts first by introducing KF 780, a highly the combined FCC-PT and ULSD applications
active and versatile CoMo grade developed for worldwide is shown in Figure 1.
FCC pretreat (FCC-PT) as well as middle distil- Research into alternative approaches to
late hydrotreating applications. KF 780 delivers the design of hydrotreating catalysts has led
enhanced metals efficiency for HDS and HDN Albemarle to introduce a new generation of cat-
activity and higher robustness in operation. alysts, Pulsar. This is a breakthrough technology

www.digitalrefining.com/article/1002300 PTQ Q2 2019 1

 2.75
2.50 DDS

2.25 DDS
S
2.00 HYD HYD-HDS
Normalised HDS activity

1.75 DDS S
HYD-HDS
1.50 S
Medium ppH2
1.25
S Low ppH2
1.00
DDS
0.75
DDS
0.50
0.25
S
0
0 10 20 30 40 50 60 70 80 90 100 110 120
ppH2, bar

Figure 2 Response to hydrogen partial pressure: DDS vs HYD-HDS

that effectively controls the morphology and dis- Therefore, DDS is necessary also in the HYD-
persion of the metal active phase. HDS route, in particular at low and medium
The first grade of this new class is KF 787 pressure (ppH2 <35-40 bar) where hydrogenation
Pulsar which delivers high activity without reactions are slow and DDS is necessary to shift
compromising stability, even in operations with the equilibrium of the first hydrogenation step.
challenging feedstock and constrained by low While at very low pressures pure DDS is the
hydrogen availability. dominant reaction, at low to medium pressure
(25 bar <ppH2 <40 bar) the DDS and the HYD-
Challenges in low and medium pressure middle HDS routes are both potentially important. The
distillates hydrotreating more refractory the sulphur species are to con-
A premium ULSD catalyst for low and medium vert, the more important will be the contribution
pressure hydrotreating applications that pro- of the HYD-HDS route.
cesses difficult feedstock requires a perfectly bal- Note that the hydrodenitrogenation (HDN)
anced combination of high activity, stability and reaction also proceeds via a hydrogenation step,
robustness against operational upsets. hence its response to hydrogen pressure and
Performance in these challenging oper- thermodynamics is similar to that of the HYD-
ations is constrained by both kinetics and HDS route.
thermodynamics. For the HYD-HDS and HDN routes to be effec-
Figure 2 shows a simplified reaction pathway tive in a hydrotreating reactor, though, addi-
for the hydrodesulphurisation (HDS) reaction tional conditions are required:
and the response of its different routes to oper- • Sufficiently high hydrogen coverage, to pre-
ating hydrogen pressure under thermodynami- serve enough hydrogen partial pressure at the
cally favourable conditions. bottom of the reactor
The HDS reaction consists of two routes. The • Sufficiently high ppH2/temperature ratio to
direct desulphurisation route (DDS) is a single avoid thermodynamic limitation of the hydro-
step reaction in which sulphur is converted via genation step
direct hydrogenation to H2S. DDS is typically the • Limited inhibition effects by refractory feed
fastest HDS pathway at very low pressure, espe- nitrogen, especially basic nitrogen, which
cially for easy sulphur removal, and is the one adsorbs on the catalyst’s hydrogenation sites and
that requires the lowest hydrogen consumption. inhibits HYD-assisted reactions
Hydrogen-assisted HDS (HYD-HDS) occurs in Based on these considerations, it is possi-
parallel with DDS and is a more complex reac- ble to identify three typical operating regimes,
tion, requiring hydrogenation (of at least one aro- or regions, for a hydrotreating reactor. These
matic ring) as a first step and DDS as a final step. regions are illustrated in Figure 3. The effective-

2 PTQ Q2 2019 www.digitalrefining.com/article/1002300

ness of the different reaction
routes varies by region:
• In the green operating region, DDS

which is characterised by a low S

temperature/hydrogen pressure
ratio, all three reactions, DDS, Red zone Green zone

Reactor temperature
HDN and HYD-HDS, are effec- DDS

tive, with DDS being dominant

for HDS at low pressure, and
S
HYD

HDN and HYD-HDS becoming

increasingly more important at DDS S

higher pressure
• In the intermediate region S

(depicted in yellow), the rates of 20 30 40 50

HDN, HYD-HDS and HDA start Reactor ppH 2, bar
to slow down because of limita-
tion of the hydrogenation steps Figure 3 Operating regions in a middle distillates hydrotreater
by thermodynamics
• In the red region, the one with the highest tem- that can still provide high robustness and full
perature/hydrogen pressure ratio, all hydro- operating stability.
genation-assisted reaction routes are severely Developing such a catalyst has been the focus
hindered. In this zone, the rate of removal of of Albemarle Catalyst Research over the last five
sulphur and nitrogen is significantly lower, and years and has required a fundamentally new
HDS has to proceed almost exclusively via the approach to catalyst design.
DDS route.
Low and medium pressure hydrotreaters pro- KF 787 Pulsar
cessing difficult feedstock often operate, totally Pulsar catalyst technology was developed
or partially, in the intermediate or in the red at Albemarle Catalysts Research Centre in
region already at the beginning of their cycles. Amsterdam. The first new grade featuring this
This is particularly true for units with very low technology is KF 787 Pulsar, a supported CoMo
ppH2, low hydrogen coverage and/or high space catalyst that is specifically designed for low
velocity, which are all conditions that lead to and medium pressure middle distillate hydro-
higher operating temperature. treating. The new catalyst is able to deliver high
In the red operating region, not only are HDS activity and stability, even in operations with
and HDN reaction rates slower, but other phe- challenging feedstock and constrained by low
nomena are also favoured and these can neg- hydrogen availability.
atively affect the performance of a catalyst. KF 787 Pulsar has a wide hydrogen pressure
Depending on a catalyst’s properties, dehydro- application range that stretches from very low
genation and condensation reactions of (nitro- to medium- to-high pressure (10-55 bar ppH2).
gen-containing) polyaromatics can occur, leading In terms of handling and sulphidation, it can be
to the formation of coke that can block the cata- treated exactly the same as the previous Stars cat-
lyst active sites. In addition, high temperature alyst generation and, like Stars, Pulsar catalysts
can cause metals migration from the active metal can be rejuvenated to over 90% of their fresh
slabs into larger agglomerates with significantly RVA HDS activity through the React treatment.
lower activity. One of the specific features of Pulsar technol-
When designing a premium catalyst for low ogy is the tightly controlled morphology and
and medium pressure for upgrading difficult size of its active metal phase. This results in
feedstock to high value diesel, all these aspects very high metal dispersion, thereby boosting
must be taken into account. The optimal catalyst metal efficiency and specific activity per reactor
would be the one that can maximise DDS activ- volume.
ity without compromising the potential of the Figure 4 shows the most widely accepted model
hydrogenating reactions for HDS and HDN, and for the hydrotreating CoMo metal active phase:

www.digitalrefining.com/article/1002300 PTQ Q2 2019 3

 treating feeds with higher end
point, more cracked stock intake
and more basic nitrogen
iii. Stability is improved thanks
to a lower tendency to form coke
on the catalyst’s surface, in par-
ticular when operating in the
intermediate and red zones.
KF 787 Pulsar’s advantages in
applications are summarised in
Figure 4 Model of the metal active slabs in CoMo hydrotreating catalysts and Figure 5, depending on its posi-
of the DDS (light green frames) and HYD-HDS active sites (dark green frames) tion in a hydrotreating reactor
and on a unit’s operating mode.
hexagonal imperfect MoS2 slabs decorated at the KF 787 Pulsar has high flexi-
S-edges with cobalt as promoter. bility in application, with respect to both the type
The HYD step of the HYD-HDS reaction path- of operation as well the loading zone in a reactor:
way takes place on the molybdenum edge and higher nitrogen tolerance allows it to be loaded
on the first ring of molybdenum atoms adjacent in the reactor top (or Zone 1); higher stability
to the slabs’ edges (molybdenum atoms in the makes it suited for the reactor’s medium and
dark green frames). In contrast, the DDS step bottom section in any (U)LSD application (Zone
occurs only on the Cobalt atoms at the sulphur 2). Equally important, its metal active phase is
edge (atoms in the light green frames). bound to the support in a way that helps prevent
Thus, when metal slabs increase in size, metal agglomeration that is typical of extended
according to their geometrical constraints, the use and exposure to high temperature. This adds
metal active slabs tend to possess progressively to the stability advantage already given by its
more HYD relatively to the DDS sites, and the high metal dispersion and DDS selectivity.
selectivity for hydrogenation increases. The special morphology and the high pres-
Reducing the size of the metal slabs, as achieved ence of DDS sites in KF 787 Pulsar’s active phase
with Pulsar technology differently, increases have been demonstrated by nitrogen monoxide
selectivity for the DDS reaction, which brings a (NO) chemisorption and by three-dimensional
number of advantages in operation at low and high resolution scanning transmission electron
medium pressure: microscopy (3D HR-STEM) measurements.
i. HDS activity increases, even in the intermedi- NO adsorbs preferentially on the cobalt atoms
ate and red operating zones (see Figure 3) at the edge of the metal slabs and can there-
ii. Nitrogen tolerance is enhanced, which allows fore be used to measure the concentration of a
catalyst’s DDS sites. As Figure
6 shows, NO chemisorption
tests have confirmed that KF
787 Pulsar has an exceptionally
Removal of easy sulphur via DDS
high concentration of DDS sites,
Low and medium pressure

Zone 1 Nitrogen and PNAs inhibit sulphur removal

KF 787 Pulsar: almost 50% more per reactor
Premium DDS activity and tolerance vs N/PNAs volume than the already highly
Removal of nitrogen via HDN (boosts HVD-HDS) DDS selective KF 780.
Removal of (hard) sulphur via DDS and/or HVD-HDS
(depending on conditions) In addition, 3D HR-STEM anal-
Zone 2 KF 787 Pulsar: ysis has shown that the active
Premium DDS activity at low ppH2 and under
thermodynamic limitation for HVD-HDS/N
metal slabs are significantly
Premium HVD-HDS/HDN activity at medium ppH2 smaller than in KF 780 and KF
757 (see Figure 7), which is in
line with KF 787 Pulsar’s high
DDS selectivity and stability.
Figure 5 KF 787 Pulsar’s advantages in middle distillate hydrotreating Microscopy analysis was carried
applications, depending on position in the reactor and operating conditions out on spent catalysts after they

4 PTQ Q2 2019 www.digitalrefining.com/article/1002300

had been tested side by side in a
pilot plant unit for 40 days. The 150

Relative NO uptake/Volume, %
test was run at low hydrogen
140
pressure (15-35 bar range) with
various feedstocks, including 130
SRGO/FCC-LCO blends and
HGO, and included a final stress 120
condition of five days with LGO
110
(1.1 wt% S; 240 ppm N; 410°C
FBP; d=0.861 g/ml) at 380°C at 100
15 bar ppH2 outlet. The objec-
tive of this final condition was to 90
apply additional stress to the cat-
80
alysts that would simulate metal KF 780 KF 787
agglomeration before analysing Pulsar
the active phase.
In Figure 7, the size distribu- Figure 6 Comparison between the concentration of DDS sites/reactor volume
tion of the active metal slabs of KF 787 Pulsar and KF 780
of KF 757 and KF 787 Pulsar is
visualised after the activity test. As can be seen, Remarkably, KF 787 Pulsar’s performance is
the active metals slabs in KF 787 Pulsar are delivered consistently across the whole middle
smaller, have a significantly narrower size distri- distillate application segment, from light SRGO
bution, and are thus also better dispersed. These applications below 20 bar ppH2, to heating oil
features are the direct result of Pulsar technology production in the 25-35 ppH2 range, to cracked
and are preserved even after long and demand- stock upgrading to high quality diesel at 50 bar
ing operating conditions thanks to a reduced ppH2. This flexibility is one of the advantages of
tendency for metal agglomeration. These obser- Pulsar technology and the result of the specific
vations are remarkable considering that the refer- design that combines high HDS activity with
ence grade is KF 757, a catalyst well known in the moderate selectivity for hydrogenation.
market for the stability of its active phase and its The gain in performance of KF 787 Pulsar
robustness in operation. can be monetised by refiners in different ways,
KF 787 Pulsar was tested extensively in pilot depending on the technical needs and the eco-
plant units with different types of feedstocks and nomics at play.
in a large range of conditions to fully assess its The most obvious utilisation would be to
applicability and performance
advantage. The results, summa-
rised in Figures 8a and 8b, con-
Probability density function

KF 787 Pulsar
firmed that it is a premium and KF 757
fully flexible catalyst by design,
suited for any ULSD middle
distillate application at low and
medium pressure, as well as
for heating oil production (50
ppmwt target product sulphur).
The RVA HDS typically ranges
from 120-130%, or up to 6°C
WABT advantage compared
with KF 780, which is among Metal slab dimension
the most active and widely
applied catalysts in the low and Figure 7 3D HR-STEM analysis of the metal active slabs in spent KF 787 Pulsar
medium pressure middle distil- and KF 757 carried out after extensive pilot plant testing, including a final
late segment. stress condition (15 bar ppH2 outlet, 380°C)

www.digitalrefining.com/article/1002300 PTQ Q2 2019 5

 DDS + HYD-HDS/N DDS + HYD-HDS/N DDS + HYD-HDS/N
LSRGO SRGO SRGO/Cracked HGO/Cracked/(Coker)
65ppm N 100-160ppm N 160-400 ppm N 750-870 ppm N
140 −6
340-400 ppm basic N
130 −5 140 −6

WABT advantage, ºC
120 −4 130 −5

WABT advantage, ºC
110 −3 120 −4
RVA HDS, %

100 −2 110 −3

RVA HDS, %
90 −1 100 −2

80 90 −1
20 30 40 50
ppH2 inlet, bar
RVA HDS 80
WABT advantage 25 35
ppH2 inlet, bar

Figure 8a Relative advantage in performance of KF 787 Pulsar vs KF 780 in RVA HDS

various middle distillate hydrotreating ULSD applications at low and medium WABT advantage
pressure
Figure 8b Relative advantage in
increase upgrading of distressed feedstock to stability that, performance of KF 787 Pulsar vs KF
ULSD, with higher density uplift as an additional in combination 780 for heating oil production (50
benefit. Considering KF 787 Pulsar’s moderate with lowered ppmwt product sulphur target) at low
selectivity towards hydrogenation, the higher SOR WABT, and medium pressure
activity would not come at cost of significantly leads to longer
higher hydrogen consumption. The high HDS cycles and thus lowered change-out and down-
activity/hydrogen consumption ratio brings low- time costs.
ered specific hydrogen consumption at equal sul- Another tangible economic advantage is KF
phur removal compared to more hydrogenating 787 Pulsar’s flexibility in operation. By fitting all
catalysts. In addition, the catalyst provides higher reactor zones in the most diverse applications it
can be utilised in any low and
medium pressure middle distil-
late hydrotreating unit, with sig-
Key features nificant advantages for refiners’
New catalyst generation catalyst pool management and
More upgrading of low
Breakthrough metal active phase value feedstock and logistics.
Metal slabs with improved morphology longer cycles Other important economic
Higher DDS/HYD selectivity and advantages are the catalyst’s
metals efficiency
Increased HDS activity / high robustness in case of oper-
H2 consumption ational upsets, energy savings
Advantages in application
in view of the potentially low-
Premium volume activity
Higher flexibility and ered WABT, and delayed capital
Superior stability even in demanding
conditions (low ppH2, difficult
robustness investments for revamping units
feedstocks, high temperature) Better risk control that are potentially constrained
High efficiency in H2 consumption by catalyst activity.
The main key features and
Increased profit from low- and mid-pressure hydrotreaters
advantages in application of KF
787 Pulsar are summarised in
Figure 9.
While KF 787 Pulsar was only
Figure 9 KF 787 Pulsar’s key features and advantages in application recently launched to the mar-

6 PTQ Q2 2019 www.digitalrefining.com/article/1002300

ket, it is already operating in its first commercial
reference. Research at Albemarle around Pulsar
technology is continuing at full speed, new appli-
cations are being explored, and future Pulsar
grades will be introduced shortly to accompany
KF 787.
Conclusions
In recent years, Albemarle has made significant
progress in the development of catalysts for low
and medium pressure middle distillates hydro-
treating. In 2015, KF 780 was introduced. It is a
highly active and versatile CoMo grade devel-
oped for both FCC-PT and middle distillate
hydrotreating with enhanced metals efficiency
for HDS and HDN activity and robustness in
operation. The acceptance of KF 780 by refiners
has been positive, with more than 12 000 tonnes
delivered and 130 operations supplied world-
wide for FCC-PT and middle distillates hydro-
treating combined.
Research into alternative approaches to hydro-
treating catalyst design and production has led to
the introduction of a new generation of catalysts,
Pulsar. This is a breakthrough technology that
allows precise control of the morphology of the
metal active phase and its dispersion. The active
metal slabs in Pulsar are smaller, better dis-
persed, and have a very narrow size distribution.
The catalysts can still be handled and sulphided
as with the previous Stars generation and, like
Stars catalysts, can be rejuvenated to over 90% of
their RVA HDS fresh activity through the React
rejuvenation treatment.
The first grade of this new generation is KF
787 Pulsar which was developed to bring high
returns primarily for refiners that process high
nitrogen and cracked feedstock, including opera-
tions constrained by low operating pressure and
limited hydrogen availability.
KF 787 Pulsar is a flexible middle distillate
hydrotreating catalyst by design. The typical
activity advantage with difficult feedstocks is
6°C WABT compared with KF 780. KF 787 Pulsar
www.digitalrefining.com/article/1002300
performs consistently across the middle distillate
application segment, from light SRGO applica-
tions well below 20 bar ppH2, to heating oil pro-
duction in the 25-35 ppH2 range, to cracked stock
upgrading to high quality diesel at 50 bar ppH2.
The performance advantage by KF 787 Pulsar
can be monetised by refiners in different ways,
depending on the technical needs and the eco-
nomics at play, starting from increased upgrad-
ing of distressed feedstock to ULSD, with higher
density uplift as an additional benefit, to longer
operating cycles leading to lowered change-out
and downtime costs.
Another tangible economic advantage derives
from the catalyst’s flexibility in operation. KF 787
Pulsar fits all low and medium pressure middle
distillate hydrotreating operations and all reactor
zones, from the top to the bottom, which greatly
simplifies refiners’ catalyst pool management
and logistics. It also offers robustness in case of
operational upsets.
Andrea Battiston is Global Market Applications Manager Clean
Fuels Technologies with Albemarle Catalysts.
Adel Abdo is Application Technologist Hydroprocessing with
Albemarle Catalysts.
Luca Moraca is Global Business Manager Clean Fuels
Technologies with Albemarle Catalysts.
Leon van den Oetelaar is Senior Scientist Hydroprocessing
with Albemarle Catalysts.
Edwin van Rooijen is Global Business Director Clean Fuels
Technologies with Albemarle Catalysts.
Henk Jan Tromp is Application Technologist Hydroprocessing
with Albemarle Catalysts.
Jelle van de Vall is Business Manager Clean Fuels Technologies
with Albemarle Catalysts.
Eelco Vogt is Professor of Refinery Catalysis at Utrecht
University and Distinguished Advisor with Albemarle.
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PTQ Q2 2019 7