Kinetic engine drives catalyst

development
Development of a NiMo catalyst for medium-to-high and high pressure middle
distillates hydrotreating
Andrea Battiston Albemarle Corporation

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Low & medium pressure

Medium-to-high and high pressure

ydroprocessing
is
an
important refinery process
for upgrading low value
HDS of easy sulphur via DDS.
feed streams to higher value
Zone
PNA conversion and HDN via HYD.
intermediates and on-specifica1
Catalyst with low affinity for the adsorption of coke precursors.
tion fuels, including ultra-low
sulphur
diesel
(ULSD).
Hydrogenation limited by nitrogen inhibition.
HDS shifts to HYD route.
Zone
Albemarles Stax kinetic model
HDN can become critical.
2
continues creating commercial
Catalyst with high HDN/HYD activity if ppH2 allows.
value by helping refiners opti
Nitrogen-inhibition-free zone.
mise hydrotreater loadings, and
Zone
has become a fundamental tool
Catalyst with high HYD activity.
3
Tune HYD activity based on operations targets and constraints.
with Albemarles research and
development for the design of
new hydrotreating catalysts.
Ketjenfine (KF) 880 Stars for
medium-to-high and high pres- Figure 1 Stax technology applied to a generic ULSD hydrotreater
sure
middle
distillates
hydrotreating is the first catalyst designed using refiner and catalyst manufacturer to design the
the Stax kinetic engine. This NiMo catalyst offers right loading scheme for each situation by taking
superior hydrogenation activity for demanding into account process objectives, economics and
operations. The benefits include higher feedstock constraints.
upgrading, increased throughput and/or cycle
In its Stax engine, Albemarle identifies three
length, improved product properties and higher main reactor zones for middle distillates hydrovolume swell. Together with the Stax technology, treating operations (see Figure 1). In zone 1, the
KF 880 brings significant advantages for the primary reactions are hydrogenation of olefins
most demanding middle distillates hydrotreating and the conversion of easy sulphur via the direct
operations.
hydrodesulphurisation (HDS) route, also called
direct desulphurisation (DDS). At the same time,
ULSD middle distillates hydrotreating: reactor polynuclear aromatics (PNA) and nitrogen species
zones and catalyst selection
start being converted via hydrogenation.
The chemical reactions and related kinetics in a
In zone 1, the main risks to operation are
hydrotreater change with the nature of the feed- condensation reactions of PNA species and coke
stock, the operating conditions, the degree of deposition. Consequently, the preferred choice is
conversion and the time on-stream. This means a catalyst that does not have too high an affinity
that applying a single catalyst load is rarely the for the adsorption of coke precursors.
optimal solution. Stax technology enables the
As the feedstock moves down the reactor, the

Catalysis 2016 1

sulphur removal rate decreases because more

refractory species need to be converted. DDS of
non-sterically hindered (di-) benzothiophenes
proceeds well into zone 2, but sulphur removal
by hydrogenation becomes increasingly important. Hydrogenation (HYD) becomes the main
HDS reaction route for refractory sulphur at
higher pressure and, in general, when hydrogenation reactions are not thermodynamically
limited.
Residual organic nitrogen inhibits the HYD
route. The faster the organic nitrogen removal,
the more effective is the removal of refractory
sulphur. At the same time di- and di+-aromatics
are further saturated to monoaromatics. Most of
the HDS and polyaromatics saturation to
monoaromatics takes place in zones 1 and 2.
Conversely, the saturation of monoaromatics to
naphthenes in zones 1 and 2 typically does not
occur as the inhibition effect by nitrogen and
PNAs is still too high.
In low and most medium pressure ULSD
hydrotreaters, Zone 2 extends to the reactor
bottom. At higher pressure or when easier feedstock is processed, on the other hand, the
hydrodenitrogenation (HDN) reaction rate can
be high enough to remove the organic nitrogen
fully, thus creating zone 3. At that point, all
hydrogenation reactions are boosted, including
that of sterically hindered sulphur. The hydrogenation of residual di- and monoaromatics is
also boosted, which can be used for additional
volume swell.

Concentration, wtppm

10000

Catalyst selection for zone 2 is the most critical

for both the operations activity and stability. If
the pressure is low or if thermodynamic limitation occurs for hydrogenation reactions, a
catalyst with a high DDS activity is preferable.
Conversely, where conditions are suitable for
hydrogenation, catalysts with a high HYD activity are preferred, as they enable much faster
removal of organic nitrogen and, with it, of
refractory sulphur.
For zone 3, catalyst selection strongly depends
on operating targets and constraints. The absence
of organic nitrogen boosts the activity of all types
of catalyst, but mostly of highly hydrogenating
ones. An additional consideration is that zone 3
may be replaced by zone 2 during the cycle as
hydrogenation activity decreases with catalyst
aging. This must be taken into account when
designing the catalyst load. Where hydrogen
availability and consumption are not limitations,
a catalyst with high HYD activity would be the
preferred solution. Conversely, where hydrogen
consumption is a constraint, or for stability
considerations, a catalyst with a lower HYD activity would be the best choice.
The right catalyst system is always the one that
best balances the operations objectives (desulphurisation, cetane uplift, volume swell, and so
on) with its limitations (ppH2/hydrogen availability, operating temperature and cycle length)
over the entire cycle.

Stax reactor zones: learning from testing

NiMo sulphur
CoMo sulphur
NiMo nitrogen
CoMo nitrogen

1000

100

10

Zone 1
1

0.1

Zone 2
0.2

0.3

0.4

0.5

Zone 3 (NiMo only)

0.6

0.7

0.8

0.9

1.0

Reactor length, (dimensionless)

Figure 2 Stax test study comparing NiMo (high HYD) and CoMo (high DDS)
Type II catalysts operation in the reactor: P=30 bar, T=350C

2 Catalysis 2016

Tests run by Albemarle highlight the effects of specific

catalyst
functionalities
on
performance in the various
reactor zones as a function of
ppH2. The HDS and HDN
results for KF 848 (Type II
Stars NiMo catalyst) and KF 757
(Type II Stars CoMo catalyst)
are shown in Figures 2 and 3. KF
848 and KF 757 catalysts are
used as references to illustrate
the behaviour of Type II NiMo
catalysts (high HYD activity)
and Type II CoMo catalysts
(high
DDS
activity),
respectively.
The figures depict the evolution of sulphur and nitrogen as

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Concentration, wtppm

SRGO (total sulphur = 1.2 wt%;

refractory
sulphur
1200
10000
ppmwt) is being converted
NiMo sulphur
along the reactor at 30 and 60
CoMo sulphur
bar inlet ppH2. The catalyst
NiMo nitrogen
1000
systems were run in parallel in
CoMo nitrogen
the same conditions and in
varying amounts to simulate
100
conversion at the different
heights in a hydrotreater. The
reference reactor length of 1.0
10
(dimensionless)
considered
here is the length needed by
Zone 1
Zone 2
Zone 3 (NiMo only)
Zone 3
1
the KF 757 system to reach 8
0
0.1
0.2
0.3
0.4
0.5
wtppm sulphur product at 30
Reactor
length,
(dimensionless)
bar.
By comparing the results, it is
possible to understand the Figure 3 Stax test study comparing NiMo (high HYD) and CoMo (high DDS)
main differences in behaviour Type II catalysts operation in the reactor: P=60 bar, T=350C
between a NiMo and a CoMo
CoMo catalyst is still more effective at removing
Type II catalyst.
When operating at moderate pressure (30 bar, easy sulphur via DDS at the reactors top, its
see Figure 2), the main route for sulphur removal higher capacity for removing nitrogen in zone 2
for most of the reactor is DDS. Because of this, a enables a NiMo catalyst to reach zone 3 much
CoMo catalyst provides a higher sulphur conver- faster, with an overall advantage in removing
sion than a NiMo catalyst, despite the higher hard sulphur. Thus, at a higher pressure, applynitrogen slip. In this case, this holds well into ing a NiMo catalyst is the best choice as HDS
and HYD of aromatics are the main targets. If
zone 2, down more than half of the reactor.
A NiMo catalyst can remove nitrogen faster hydrogen consumption is a specific constraint, a
than a CoMo catalyst, which can boost sulphur CoMo catalyst can still be applied at the reactor
removal via the HYD route when approaching bottom under the NiMo catalyst to limit the
the reactors bottom. In this case, the NiMo cata- saturation of di- and monoaromatics.
As mentioned previously, being able to reach
lyst even reaches a nitrogen-free zone (zone 3) in
view of the easy feedstock utilised. However, the zone 3 has a significant impact on HDS and on
advantage of the overall process remains limited the saturation of residual di- and monoaromatmainly because the ppH2 is low, so that at the ics. Monoaromatic saturation, in particular, is
end the CoMo and the NiMo catalysts reach very difficult and is significantly inhibited by the
basically the same HDS performance for ULSD nitrogen still present in zone 2, so incremental
monoaromatic saturation occurs primarily in
production.
The case illustrated is boundary for the use of zone 3. Hence, when hydrogen consumption is
either a CoMo or a NiMo catalyst. With more not a constraint and cetane uplift and volume
difficult feedstocks, at low pressure the nitrogen swell are the operating targets, applying a catalevel remains higher down to the bottom of the lyst system capable of creating and maintaining
reactor. Also, for a NiMo catalyst, zone 3 cannot a larger zone 3 at the reactor bottom will bring a
be reached. As a result, the HYD reaction route significant advantage by generating additional
is significantly less effective and a CoMo catalyst high value diesel through cetane uplift and
typically delivers an overall better performance volume swell.
for ULSD. Also, in terms of stability a CoMo
catalyst is preferable at low pressure.
Stax technology at work:
When operating at higher pressure (60 bar, commercial experience
see Figure 3), it is advantageous to apply a cata- Two case studies illustrate how refiners have
lyst with a higher HYD activity. Although a successfully applied Albemarles Stax technology

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Catalysis 2016 3

KF 757

Cycle 1

KF 767

KF 767 Stars (high HYD CoMo) to

lower nitrogen from the top.

KF 860
KF 848

KF 860 and KF 848 Stars (NiMo) to

maximise HDN and HDS.

KF767

KF 767 Stars for HDS, stability and

to limit H2 consumption.

Cycle 2

Figure 4 Commercial case A - comparison between catalysts loading in

cycles 1 (CoMo) and 2 (Stax CoMo/NiMo/CoMo)
Commercial case A - comparison between operations in cycles 1 and 2
Case A
Feed composition and properties
LCO + VBGO, vol%
Sulphur, wt%
Nitrogen, ppmwt
Density, g/ml
Operating parameters
ppH2 inlet, bar
H2/oil ratio, NL/L
Avg. total feed rate, %, normalised

Cycle 1

Cycle 2

5 + 1 (6)
0.94
202
0.860

5 + 1 (6)
0.95
213
0.858

54
170
100

58
177
102.5

Table 1

410
400

WABT, C

390
380
370
360
350
340

Cycle 1
Cycle 2

330
320

10

12

14

16

18

20

22

24

Time on stream, months

Figure 5 Case A - comparison of the start-of-run WABT and the cycle length
between cycles 1 and 2

4 Catalysis 2016

to increase their operating

margins.
Case A is a medium-to-high
pressure ULSD operation treating a blend of straight run gasoil
and cracked feedstock. The
refinery used to operate with KF
757 Stars, a CoMo catalyst with
high DDS activity. The main
reason for selecting KF 757 was
to guarantee stability in view of
the moderate ppH2 at reactor
bottom.
The optimisation strategy for
the new cycle (see Figure 4,
Cycle 2) has been to increase the
overall hydrogenation activity
within
the
operations
constraints while still guaranteeing sufficient stability over the
cycle. A high performance Stax
CoMo/NiMo/CoMo configuration was used, operating with
similar conditions and feed
properties as in the previous
cycle (see Table 1, Cycle 1).
KF 767 CoMo catalyst was
used for the upper section, as
inhibition by nitrogen was not
too high, to start lowering the
nitrogen slip at an early stage.
A combination of KF 848 and
KF 860 high hydrogenation
activity NiMo catalysts was
used in the middle section,
where the ppH2 was still high
and the additional hydrogenation activity would accelerate
nitrogen removal and tackle
refractory sulphur most effectively. KF 767 catalyst was
preferred over a NiMo in the
lower section to limit H2
consumption and to preserve
the
operations
stability
throughout the cycle.
The new system lowered
the start-of-run temperature
(WABT) by approximately 20C,
which also allowed an increase
in the overall stability of the
operation. The cycle length was

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more than doubled as a result

(see Figure 5).
Case B is a medium-to-high
pressure hydrotreater that was
KF 860 Stars (NiMo) to boost HDN and
revamped by Albemarle and its
KF 860
KF 757
guarantee stability at the top.
Alliance partner UOP to meet
the refinerys growing diesel
demand. The revamp lead to an
increase of over 30% in the
KF 868
KF 868 Stars (high HYD NiMo) to
units capacity. The operating
enlarge zone 3 and boost volume
KF 868
hydrogen pressure was also
swell.
slightly increased.
KF 767
To capture maximum advantage from the revamp, Stax
technology was used to design
the new catalyst system. A KF
757/KF 868/KF 767 Stax (CoMo/
Cycle 1
Cycle 2
NiMo/CoMo) load, which had
provided
good
performance Figure 6 Commercial case B - comparison between catalysts loading in cycles 1
before the revamp, was changed (Stax CoMo/NiMo/CoMo, before revamp) and 2 (Stax NiMo, after revamp)
out for a KF 860/KF 868 Stax
(NiMo) system designed to
Commercial case B - comparison between operations in cycles 1 and 2
upgrade more heavy cracked
components to diesel. The stratCase B
Cycle 1
Cycle 2
egy in this case was to remove
Feed composition and properties
LCO, vol%
2
8
nitrogen as fast as possible in
LCGO,
vol%
18

19
zone 2 to enable a substantial
Nitrogen, ppmwt
240
332
zone 3 operation for the unconDensity, g/ml
0.854
0.860
strained
hydrogenation
of
Operating parameters
ppH2 inlet, bar
46
52
refractory sulphur and of di- and
H
/oil
ratio,
NL/L
460

360
2
monoaromatics. A comparison
Avg. total feed rate, %, normalised
100
125
between the loaded systems and
operating parameters in cycles 1
(CoMo/NiMo/CoMo,
before Table 2
revamp) and 2 (NiMo, after
revamp) is shown in Figure 6 and Table 2, cation of the new Stax design was an increase in
the total feed rate of over 25% and an even higher
respectively.
The main result of the revamp and of the appli- intake of distressed feedstocks. In particular, over

Light cycle oil (LCO)

intake, t/h

Light coker gasoil

(LCGO) intake, t/h

60
50
40
30
20
10
0

30

60

90

120

150

Time on stream, days

180

30

Cycle 1
Cycle 2

25
20
15
10
5
0

30

60

90

120

150

180

Time on stream, days

Figure 7 Case B - comparison of the cracked stock intake during cycles 1 and 2 (first 180 days; cycle 2 is still running). Albemarles incumbency has already been reconfirmed for the next cycle

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Catalysis 2016 5

Stars, Albemarles NiMo reference catalysts, is summarised

in Figure 8, as derived from
+30 to 35%
vs KF 848
RVA
pilot plant test results with
HDN
+20%
vs KF 868
various feedstocks in the
Density +3.0 to 3.5 g/l vs KF 848
7080 bar ppH2 inlet range.
reduction +2.0 to 2.5 g/l vs KF 868
KF 880 Stars catalyst
A test comparing KF 880
In addition to optimising reac- Figure 8 Average performance
with KF 848, both as full loads
tor loading using existing advantage of KF 880 Stars catalyst
on HGO at 80 bar ppH2 inlet,
catalysts, Stax technology is compared with KF 868 and KF 848
hydrogen/oil ratio = 500 NL/L
currently used by Albemarle Stars catalysts
and 341C, shows KF 880s
R&D to support new catalyst
significantly higher HDS, HDN
design.
and HDA activity in zones 2 and 3 (see Figure
KF 880 Stars, Albemarles new supported 9). Sulphur conversion in the test was increased
NiMo grade for medium-to-high and high pres- by decreasing space velocity.
sure middle distillates hydrotreating, is the first
The advantage in density reduction of KF 880
catalyst created using the Stax catalyst engine. starts developing in zone 2 (+2.0 g/L) as a result
KF 880 is Albemarles highest performance of its superior hydrogenation activity and peaks
NiMo catalyst with increased hydrogenation in zone 3 (+3.9 g/L) where the nitrogen inhibiactivity to boost removal of nitrogen and refrac- tion on aromatics saturation has been fully
tory sulphur, and aromatics saturation.
removed.
The sweet spot application for KF 880 Stars
In zone 1, KF 861 NiMo catalyst would be the
catalyst is in zones 2 and 3 in medium-to-high preferred choice, as it offers the same perforand high pressure operations, where sufficient mance at the reactors top but at reduced cost
ppH2 is available and superior hydrogenation for refiners. Note that loading up to 30 vol% KF
activity is required. KF 880 Stars catalyst can be 861 catalyst at the top of the reactor has a negliapplied to a wide range of value propositions, gible impact on the activity of the overall catalyst
including upgrading distressed feedstock to system.
ULSD, volume swell and increased feed throughput and cycle length.
Superior hydrogenation activity in middle
The performance advantage of KF 880 Stars distillates hydrotreating
catalyst compared with KF 868 and KF 848 Stax solutions for medium-to-high and high
pressure
middle
distillates
applications where high hydrogenation activity is required are
Zone 2
Zone 3
1000
summarised in Figure 10.
KF848
KF 861 catalyst is Albemarles
KF880
choice for zone 1, as it delivers
high activity and stability at the
100
reactor top at a reduced cost.
The main NiMo catalysts to be
applied in zones 2 and 3 are KF
868, as a base case, and KF 880,
10
Albemarles
new
supported
KF 880 vs KF 848
NiMo option. As shown, KF 880
Product nitrogen: 25 vs 40
4 vs 12
<0.3
catalyst delivers boosted HYD
Density, g/l:
+0.3
+2.0
+3.9
activity that can be used by
1
0
5
10
15
20
25
30
refineries seeking higher feedTime on stream, days
stock
upgrading,
improved
product properties and addiFigure 9 Pilot plant test results of KF 880 compared with KF 848 Stars
tional volume swell to improve
catalyst
operating margin.
RVA
HDS

+20 to 25%
+15%

vs KF 848
vs KF 868

Product sulphur, ppm

30% more high density and

poor cetane LCGO and over
350% more LCO components
were fully upgraded to valuable
Euro V diesel (see Figure 7).

6 Catalysis 2016

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In addition, Nebula catalyst

can be applied in Stax combinations starting from deep zone 2
and zone 3. Because of its
Zone 1 Apply catalyst with low affinity for PNA adsorption.
KF 861
unique active site density,
Balance
Nebula provides extremely high
HYD activity. When Nebula is
KF 868
placed higher in the reactor, its
Zone 2 Apply catalyst with high HDN/HYD activity.
KF 880
Boost
additional activity can be
Nebula
exploited to maximise HDN and
HDS performance. Alternatively,
KF 868
when the catalyst is placed at
Zone 3 Apply catalyst with high HYD activity.
KF 880
Boost Exploit cetane uplift and volume swell.
the reactors bottom, it yields
Nebula
increased monoaromatics saturation, cetane uplift and volume
swell. The benefit for HDS
remains.
Albemarle has developed and Figure 10 Stax solutions for medium-to-high and high pressure middle
is continuously refining Stax, its distillate applications to deliver high hydrogenation activity
proprietary kinetic model and
reactor load optimisation technology, which is a variety of distillates hydroprocessing applications. He has held
positions with various responsibilities in catalyst research and
routinely used for the development of new
development, laboratory testing and application technology. He
catalysts.
holds a MSc degree in chemical engineering from Politecnico
KF 880 Stars, Albemarles top-performing di Milano, Italy, and a PhD in heterogeneous catalysis and
NiMo grade for medium-to-high and high pres- spectroscopy from Utrecht University, The Netherlands.
sure middle distillates hydrotreating, is the first
catalyst designed with the direct support of the
Stax kinetic platform. It offers increased hydrogenation activity for refiners seeking higher
LINKS
feedstock upgrading, improved product properties and volume swell.
More articles from: Albemarle Corporation
Andrea Battiston is a Senior Technical Specialist Hydroprocessing
with Albemarle Corporation, providing support to the companys
global Clean Fuels Technology business and technical groups in

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More articles from the following categories:

Catalysts and Additives
Sulphur Removal, Recovery and Handling

Catalysis 2016 7