Impact of sulphiding agents on ULSD

catalyst performance
A research programme demonstrated the comparative performances of a conventional
sulphiding agent and an agent that offers safer, cleaner catalyst activation

TIAGO VILELA, JOSÉ CASTRO and HENDRIK DATHE

Avantium

T
he purpose of this research all catalysts while reaction tempera- required cooperation and simulta-
was to compare the hydropro- tures were varied. neous alignment of interests among
cessing performance of three Evaluation of the differences in multiple world-leading vendors:
different commercially available performance between catalysts is • Lubrizol1 provided expertise, sul-
cobalt-molybdenum (CoMo) cata- not part of this study and therefore phiding agents, and funding
lysts in two sets of circumstances: not reported here. For each of the • Catalyst vendors provided cata-
(a) after activation with Lubrizol’s catalysts evaluated, results indi- lyst and process expertise, catalyst
SulfrZol 54 (SZ54) and cated that sulphiding with SZ54 samples, and approval of the test-
(b) after activation with dimethyl delivered the same level of HDS as ing protocol. The catalysts samples
disulphide (DMDS). sulphiding with DMDS. For achiev- were supplied by world leader cat-
SZ54 is a sulphiding agent ing 10 wtppm sulphur, activity dif- alysts manufacturers from Europe
commercialised by Lubrizol ferences between catalysts activated and the US
Corporation for the activation of with the two sulphiding agents • Avantium2 provided project man-
hydroprocessing catalysts. This were <0.3°C, which is within the agement, high-throughput catalyst
alternative to traditional sulphiding typical repeatability for hydropro- testing technology, testing expertise,
agents offers a higher flash point, cessing catalyst activity tests (usu- and funding.
low odour, and emissions improv- ally about 1°C). Positive relationships developed
ing technology, which results in In addition to product sulphur, during Avantium’s previous expe-
safer, cleaner, and effective catalyst other important performance indi- rience with all parties proved to be
activation to refineries. cators were evaluated: product crucial during the alignment of pro-
CoMo hydrotreating catalysts and nitrogen, hydrogen consumption, ject participants.
input on procedures were provided liquid product density, and light
by the participating catalyst ven- end yields. In each case, results con- The sulphiding step
dors. Two samples of each catalyst firmed that sulphiding with SZ54 is Commercial hydrodesulphurisa-
were activated, one with DMDS and technically equivalent to sulphiding tion (HDS) employs catalysts in
the other with SZ54. with DMDS for hydrotreating mid- which the active species are molyb-
The feed was a straight-run gas- dle distillates in order to produce denum or tungsten sulphides pro-
oil (SRGO) with 1.444 wt% sulphur, ultra low sulphur diesel (ULSD). moted by cobalt or nickel sulphides.
173 wtppm nitrogen, 28.2 wt% Some aspects of this research may Production of ULSD typically is
aromatics, and SimDist distilla- lead the way to improved sulphid- accomplished by HDS over CoMo
tion range (0.5% to 95%) of 92°C to ing technology. or NiMo catalysts. During HDS,
391.4°C. hydrodenitrogenation (HDN) and
A common range of operating Background saturation of olefins and aromatics
conditions for the tests was selected Lubrizol sought independent con- also occurs.3,4
after consultation with the catalyst firmation of previous comparisons Most often, the catalysts are deliv-
vendors. Testing was performed of DMDS vs SZ54 performance for ered as oxides and activated by
by Avantium using a combina- commercial hydrotreating catalysts reductive sulphidation (sulphiding)
tion of advanced high-throughput activation. In addition to seeing in the presence of hydrogen at ele-
testing equipment, robust exper- benchmarks for sulphiding agent vated pressure. Sulphur can be sup-
imental design, and extensive behaviour, catalyst and technology plied in different ways: as H2S, with
technical expertise. Performances suppliers saw how independent the native sulphur in a feedstock, or
were measured simultaneously testing matched their catalyst per- as a sulphur spiking agent. Spiking
using Avantium’s multi-reactor formance expectations. agents include DMDS, dimethylsul-
Flowrence parallel testing technol- phoxide (DMSO) and SZ54, which
ogy. During the activity test, pres- Project participation contains di-t-butylpolysulphide
sures and flows were the same for This unique and challenging project (DBPS).5

www.eptq.com Catalysis 2019 11

 ing recycle gas. During a purge,
Comparison of DBPS and DMDS5
the methane, along with valua-
ble hydrogen and even sometimes
Property DBPS DMDS H2S, is routed to the flare. (Usually,
Hydrocarbon from decomposition i-butane + H2S Methane + H2S purges of sour recycle gas are amine
Destination of decomposition hydrocarbon Alkylation unit Fuel gas
Sulphur content, wt/wt% 54 68 scrubbed before they reach the flare.
Initial decomposition temperature 320°F (160°C) 392°F (200°C) If not, a purge can generate unde-
Flash point (closed cup) 212°F (100°C) 61°F (16°C) sired SOx.)
Odour description (vendor) Low odour (like diesel) Unpleasant garlic-like odour • Odour. DMDS has an unpleas-
ant odour. Even small leaks can be
Table 1 a nuisance to refinery workers and
the surrounding community. In
(There are noteworthy exceptions that DBPS has a higher flash point, contrast, SZ54 is less volatile and
to the need for in situ sulphiding. lower odour, lower initial decom- possesses a far less offensive, die-
Presulphurised catalysts include position temperature, and lower sel-like smell.
the actiCAT products offered by emissions. • Transport regulations. Due to its
Criterion Catalysts & Technologies,6 low flash point, shipment of DMDS
and catalysts that are presulphided Advantages of SZ54 is regulated by the US Department
with the Totsucat technology When compared to DMDS, SZ54 of Transportation (DOT) and simi-
offered by Eurecat.7) has the following advantages5: lar organisations in other jurisdic-
Sulphiding is one of the most crit- • Safety. Due to the higher flash tions. Often, DMDS trucks must be
ical aspects of fixed bed commercial point of SZ54 – 212°F (100°C) vs continuously supervised. In con-
hydroprocessing. Process upsets 61°F (16°C) for DMDS – it presents trast, the US DOT classifies SZ54 as
during catalyst sulphiding can have less of a fire hazard. SZ54 requires non-hazardous for transportation.
deleterious consequences.8 no special packaging, transporta-
The sulphur in feedstocks and tion, or storage requirements. In Experimental programme
spiking agents is converted into contrast, DMDS usually is stored The experimental programme com-
H2S, which in turn reacts with the under nitrogen pressure in closed pared the performance of three dif-
catalytic oxides. Relevant chemical containers. ferent commercial CoMo ULSD
reactions include the following: • Co-produced hydrocarbon. SZ54 catalysts after sulphiding with
has a major economic plus: in SZ54 (which is comprised mostly
Sulphur-containing gasoil + H2 → sulphur-lean addition to H2S, it yields primar- of DBPS) and after sulphiding with
gasoil + H2S ily isobutane, which is a high- DMDS. Avantium received catalyst
Spiking agent + H2 → hydrocarbon + H2S value refinery intermediate stream samples from each vendor in the
1. CH3-S-S-CH3 + 3 H2 → 2 CH4 + 2 H2S required for alkylation. As sulphid- form of extrudates with diameters
2. C4H9-S-S-C4H9 + 3 H2 → t-C4H10 + 2 H2S
ing with SZ54 proceeds in a hydro- between 1.6mm and 1.8mm.
processing unit, the isobutane is
Sulphiding reactions1 easily isolated from the hydrogen Feedstock
3. MoO3 + 3 H2S + H2 → MoS2 + 3 H2O rich recycle gas. The straight-run gasoil (SRGO)
4. WO3 + 3 H2S + H2 → WS2 + 3 H2O In contrast, DMDS yields meth- used for sulphiding and for the test
5. 3 NiO + 2 H2S + H2 → Ni3S2 + H2O ane, which accumulates in the recy- came from a commercial refinery.
6. 9 CoO + 8 H2S + H2 → Co9S8 + 9 H2O cle gas, decreasing hydrogen partial SRGO properties are presented in
pressure (ppH2). Often, the ppH2 Table 2. Note that the sulphur con-
Unwanted reduction of nickel oxide gets so low that the methane con- tent is 1.44 wt% and the nitrogen
7. NiO +H2 → Ni(m) +H2O tent must be decreased by purg- content is 173 wtppm. For sulphid-
ing, the SRGO was spiked with
Questions exist about the exact SZ54 or DMDS to reach a total sul-
Straight-run gasoil feed for sulphiding
stoichiometry of Reactions 5 and and testing
phur of 3 wt%.
6.7,9 Regardless, successful activa-
tion requires excess H2S, excess Testing equipment
Property SRGO
H2, and close adherence to pro- Sulphur, wt% 1.444 For this evaluation, Avantium used
cedures developed by catalyst Nitrogen, wtppm 173.2 a testing unit with 16 parallel sin-
manufacturers. Hydrogen, wt% 13.07 gle pellet string reactors (SPSR).
SG 60/60°F, g/ml 0.8538
The equipment layout is illustrated
Aromatics, wt% 28.2
Properties of DBPS and DMDS T5, °C 181.2 by the schematic diagrams shown
DMDS is the most widely used sul- T30, °C 273.0 in Figures 1 and 2 (one or more pat-
phur spiking agent for activating T50, °C 306.6 ents apply).10 The unit employs
hydroprocessing catalysts. Table 1 T70,°C 335.0
Flowrence technology, which pro-
T95, °C 391.4
compares DMDS with an approved vides tight control of process con-
alternative: DBPS, the main con- ditions – temperature, flow rates,
stituent of Lubrizol’s SZ45. Note Table 2 and pressure. The system provides

12 Catalysis 2019 www.eptq.com

Figure 1 Schematic representation of the Avantium pilot plant with 16 parallel SPSR

for accurate measurement of yields,

hydrogen consumption, and prod-
uct properties.
Moonen et al (2017)11 found
that for gasoil hydroprocessing,
there is excellent correspondence
between results from an Avantium
SPSR unit and those from a bench-
scale unit with a catalyst volume
of 225 ml. Their experiments con-
firmed that SPSR are no more
susceptible to wall effects, chan-
nelling, and back-mixing than the
much larger reactors. The authors
explained the similarity with rigor-
ous modelling of the corresponding
hydrodynamics.

Practical advantages of SPSR

Traditional hydroprocessing pilot
plant studies employ relatively
large reactors, typically with an
inside diameter (ID) ranging from
1.2-2.5cm and a catalyst bed length
of 30-80cm. Consequently, within a
limited budget and tight timeframe,
it becomes impractical to evaluate Figure 2 Schematic diagram of reactor and effluent set-up

www.eptq.com Catalysis 2019 13

 more than a few alternative catalysts 300mm length and 2mm internal
or sets of process conditions – in this diameter. The void volume between
case, alternative sulphiding agents. the catalysts was filled with the
Associated with series tests are ceramic beads to prevent channel-
inherent uncertainties, for example, ling, wall effects, and back-mixing.
due to differences in catalyst load- A second bed of ceramic beads was
ing. Replicate tests, which can min- added at the top until the reactor
imise such uncertainties, are seldom was completely filled.
even considered. In a conventional Exceptionally precise loadings
pilot plant, the research described can be achieved. In this study, four
in this article would have required reactors were loaded with each one
several barrels of feed and 32 sepa- of the three catalysts for a total of
rate month-long runs. 12 reactors loaded into the unit.
In contrast, parallel small-scale For the catalyst weights, the aver-
testing in SPSR significantly reduces age deviation was just 0.1 wt% (see
feed and catalyst requirements. It Figure 4).
also reduces labour and utilities
costs. Most significantly, it provides Catalyst activation (sulphiding)
a way to accomplish more in a given Catalyst activation (sulphiding) was
amount of time. Reactor loading Figure 3 Reactor loading schematic accomplished in two campaigns. In
is more reproducible because the the first campaign, half of the reac-
diameter of the extrudates is slightly tors were sulphided using DMDS
smaller than the reactor diameter; Reactor loading and in the second using SZ54. The
extrudates automatically line up in The weights of catalyst for this study same activation procedure was fol-
strings (see Figure 3). The narrow- were calculated using the compact lowed for sulphiding each catalysts
ness of the reactors decreases mald- bulk density (CBD) provided by the with both agents. Same pressure,
istribution of gas and liquid over the vendors. A bottom section of ceramic gas/oil ratio, and space velocity
catalysts, thereby preventing cata- beads (50-200µm diameter) was sup- were used for the activation of all
lyst bed channelling and incomplete ported by a small frit (20µm pore catalysts (see Table 3), however
catalyst wetting. An inert diluent diameter). Above the support beads, different temperature ramps were
can be introduced after catalyst pel- stacks of catalyst extrudates were used for the activation of each cat-
lets are loaded to further increase loaded into the isothermal section, alyst following the vendors’ guide-
flow distribution and wetting. which has the following dimensions: lines. Temperature programmes for
the catalysts activation are not pre-
sented for confidentiality reasons,
1.0 however these were representative
of common activation procedures
Catalyst weight relative error,

0.8
followed in refineries.
0.6
The catalysts were dried at 50°C
0.4 under flowing nitrogen for one
0.2 hour before the introduction of
0 feed. After drying, all catalysts were
soaked with the sulphiding feed for
−0.2
four hours at space velocity 3 h-1.
−0.4
The catalysts were sulphided with
−0.6 the SRGO+DMDS feed using the
operating conditions presented in
wt%

−0.8
−1.0 Table 3. At each sulphiding stage,
1 2 3 4 5 6 7 8 9 10 11 12 the temperature of each heating
Reactor block was controlled independently.
This allowed the simultaneous use
Figure 4 Relative error during catalysts loading of different temperature programs
for sulphiding the three different
Operating conditions for sulphiding and the evaluation test
catalysts. After sulphiding, the unit
was cooled to 30°C and flushed
with un-spiked SRGO and then N2
Operating condition Soaking Sulphiding Evaluation tests
H2 pressure, barg 45 45 55
to remove any remaining traces
LHSV, h-1 3 2 1.5 of H2S. Then the reactors were
H2/oil ratio, Nl/l 50 300 300 removed from the unit and stored
safely while minimising any contact
Table 3 with air.

14 Catalysis 2019 www.eptq.com

 Catalysts loading matrix Test schedule and analysis per condition

Catalyst DMDS SZ54 Test condition Duration (days) Offline analysis Mass balance check
A R1 & R3 R2 & R4 Line out 10 1 S, 1 N per day 2 /day
B R5 & R7 R6 & R8 Condition 1: Target = 50 wtppm S 4 Same as above 2 /day
C R9 & R11 R10 & R12 Condition 2: Target = 100 wtppm S 4 Same as above 2 /day
Condition 3: Target = 10 wtppm S 4 Same as above 2 /day
Table 4 Condition 4: Back check Condition 1 3 Same as above 2 /day

In the second campaign, sul- Table 5

phiding was accomplished with
the SRGO+SZ54 blend following
the exact same procedure. Again, 160
Catalyst A − SZ54
after sulphiding, the reactors were 140

Sulphur in product, wtppm

Catalyst A − DMDS
cooled, flushed, and removed from 120
the unit avoiding exposure to air.
Special measures were applied 100

to minimise contact with air dur- 80

ing the storage and subsequent re- 60
installation of reactors containing
sulphided catalysts. 40

20
Catalyst performance tests 0
Six reactors from each sulphid- T0_A T0_A T0_A T0_A T0_A T0_A T0_A
ing batch were loaded into the unit +5ºC +10ºC +15ºC +20ºC +25ºC +30ºC
Temperature, ºC
according to the matrix shown in
Table 4. That is, each heating block 200
Catalyst B − SZ54
contained two identically loaded 180 Catalyst B − DMDS
and sulphided reactors. The dupli-
160
cation provided a back check to
minimise concerns about whether 140
Sulphur in product, wtppm

or not results from any particular 120

reactor might be spurious.
100
Immediately after reinstallation,
the reactors were flushed with N2 80

to remove any traces of air or mois- 60

ture picked up by the catalysts
40
during the reactors installation pro-
cedure. The operating pressure 20

was adjusted to 55 barg at a rate of 0

T0_B T0_B T0_B T0_B T0_B T0_B
0.5 barg/min and then the reactors T0_B
+5ºC +10ºC +15ºC +20ºC +25ºC +30ºC
were soaked with the testing feed Temperature, ºC
(SRGO) at the same conditions used
200
previously for sulphiding. Catalyst C − SZ54
180 Catalyst C − DMDS
Product analysis 160
Reactor outlet gas compositions
140
were analysed by online gas chro-
Sulphur in product, wtppm

matography (GC). Helium (the 120

internal standard) and H2 were 100
measured with a thermal conduc-
80
tivity detector (TCD). Hydrocarbons
were quantified with a flame ionisa- 60
tion detector (FID). The liquid efflu- 40
ent was collected continuously for 20
eight hours twice per day. The sam-
ples were weighed offline, and the 0
T0_C T0_C T0_C T0_C T0_C T0_C
T0_C
weight results were automatically +5ºC +10ºC +15ºC +20ºC +25ºC +30ºC
coupled with the online GC results Temperature, ºC
to determine material balance.
Total sulphur and nitrogen were Figure 5 Sulphur product results

www.eptq.com Catalysis 2019 17

 with a six-day stabilisation (line
0 out) period to ensure a proper sta-
Catalyst B − DMDS
−0.2
bilisation of the active sites on the
Catalyst B − SZ54
catalysts. After this, three different
−0.4 temperature conditions were eval-
−0.6 uated with a duration of 3-4 days
each. Finally, a back check or return
−0.8
point was performed at the end of
−1.0 R2 = 0.9934 the run in order to verify the rela-
tive activity of each catalyst.
ln(K_HDS)

−1.2
The sulphur and nitrogen con-
−1.4 tents of liquid products from each
−1.6
R2 = 0.9991 reactor were measured daily. With
Temperature-1, ºK-1 online GC, each product gas stream
was monitored continuously. For
material balance calculations, liq-
uids from each reactor were accu-
0 mulated twice per day for eight
Catalyst A − DMDS hours each time.
−0.2 Catalyst A − SZ54
−0.4 Test results
−0.6
Product sulphur
Figure 5 shows the product sul-
−0.8 phur results determined during the
−1.0
R2 = 0.9928 performance test for each catalyst.
Recall that the runs were made in
ln(K_HDS)

−1.2
duplicate: two different reactors
−1.4
R2 = 0.9979
were loaded with the same catalyst
−1.6
in all cases in order to evaluate the
Temperature-1, ºK-1 reproducibility of the results. The
reproducibility was superb: differ-
ences between all duplicates were
0 less than 5% and most differences
Catalyst C − DMDS
−0.2
at ULSD conditions were less than
Catalyst C − SZ54
1 wtppm.
−0.4 The level of desulphurisation
−0.6 reached during the evaluation
was between 99% and 99.9%. This
−0.8
implies that the identification of
−1.0 differences in catalysts HDS per-
formance as presented in Figure 5
ln(K_HDS)

−1.2 R2 = 0.9997
required a very high accuracy from
−1.4 the experimental set-up.
R2 = 0.9992
−1.6 Even though the catalysts were
Temperature-1, ºK-1 provided by different vendors, all
of them showed similar compara-
Figure 6 Basis for kinetic parameters estimation for HDS tive performance when sulphided
with SZ54 and DMDS. All cata-
analysed with a TN/TS 3000 S/N The reactors pressure was con- lysts sulphided with SZ54 showed
analyser, which has a detection limit trolled to 55.0 barg. The flows of a slightly lower HDS capacity
of around 2 ppm ±0.2 ppm. liquid and gas to the reactors were (compared with the same catalyst
Density measurements were per- tightly controlled at the specified set sulphided with DMDS) when oper-
formed with a Mettler Toledo DM50 points, allowing an average mass ated at the 100 ppm sulphur target
unit. balance closure of 99.94±0.4%. condition. This difference was even
Calculated flow based parame- smaller during the 50 ppm sul-
Operating conditions ters were LHSV = 1.5 h-1 and H2/oil phur target condition and basically
Catalyst vendors estimated reac- ratio = 300 Nl/l. none when the catalysts were oper-
tion temperatures for reaching ated at ULSD conditions (<20 ppm
product sulphur contents of 10, 50 Testing protocol sulphur product). The difference
and 100 wtppm for their respective A summary of the testing protocol in response observed for all cata-
catalyst. is shown in Table 5. The test began lysts in Figure 5 seems to indicate

18 Catalysis 2019 www.eptq.com

 tion commercial unit, as the sul-
phiding agent does not seems to
DMDS SZ54
TBASE affect the performance of the cata-
+1ºC lyst at high HDS conditions.
10 ppm sulphur in product
Temperature required for
TBASE On the other hand, the differ-
TBASE ences observed in the activation
−1ºC energy for catalysts sulphided with
SZ54 may lead to further studies by
Lubrizol and catalysts vendors in
order to optimise the operating con-
ditions for the catalysts activation.
Usual hydroprocessing catalysis
activation procedures are based on
Catalyst A Catalyst B Catalyst C the use of DMDS which present a
higher decomposition temperature
Figure 7 Temperatures required for 10 wtppm product sulphur and different physical properties.

Activation energy estimates Temperature required for 10 wtppm

product sulphur
Figure 7, which is based on the kinetic
Catalyst Ea (kJ/mol) Sulphided w/ DMDS Ea (kJ/mol) Sulphided w/ SZ54
Catalyst A Base Base + 18.44 parameters, shows temperatures
Catalyst B Base Base + 21.53 required to achieve 10 wtppm prod-
Catalyst C Base Base + 11.03 uct sulphur. The difference between
sulphiding agents is very low: <0.3°C
Table 6 for all catalysts. As can be seen in
Figure 7, the error bar estimated from
the measurement of repeated experi-
Other product properties comparison (@ 10 ppm sulphur target conditions) ments (duplicated reactors) is in most
cases higher than the difference in
Average difference @ 10 ppm sulphur target
performance between the catalysts
Property Range Cat A Cat B Cat C sulphided with different agents. This
Nitrogen, wtppm 0.3-0.6 -0.03 0.03 0.02 enables the conclusion that each cat-
Density, g/ml 0.8326-0.83334 -0.0001 -0.0006 0.0000 alyst sulphided with the different
H2 consumption, m3 H2/m3 feed 55-63 4 2 0
Light end yield, wt% 0.64-0.87 -0.02 0.01 -0.03
agents will reach 10 wtppm product
sulphur at a similar SOR temperature
with an uncertainty (95% confidence
Table 7 level) of less than ±1°C.

slightly different HDS activation arly and inversely proportional to Other product properties
energies depending on the sulphid- the absolute temperature. The slope Table 7 shows a comparison of all
ing agent used for the catalysts of the line is Ea/R, where Ea is the other product properties measured
activation. activation energy and R is the ideal during the tests for the catalysts
In any case, the results presented gas constant. Figure 6 presents the sulphided with each agent. In gen-
in Figure 5 clearly demonstrate that graphs from which activation ener- eral, no significant differences were
catalysts sulphided with SZ54 show gies (Ea) were determined. For each observed for nitrogen, liquid den-
the same level of desulphurisation catalyst, the coefficient of determina- sity, hydrogen consumption, and
as catalysts sulphided with DMDS tion (r2) is excellent: all were above light end yields production inde-
when compared at ULSD produc- 0.99. The relative comparison of the pendently of the sulphiding agent
tion operating conditions. Ea values is given in Table 6. used.
Activation energy is a meas-
Kinetic parameters ure of sensitivity to temperature. Conclusions
Kinetic parameter estimates were Therefore, this research indicates This research compared the hydro-
based on plots developed from the that catalysts sulphided with SZ54 processing performance of three
product sulphur values obtained seem to be more temperature sen- commercial CoMo catalysts from
during Condition 1 (50 ppm sulphur sitive than those sulphided with three different vendors in two sets
target), Condition 2 (100 ppm sul- DMDS. This result does not have of circumstances: (a) after activation
phur target) and Condition 3 (100 any direct implication for the per- with Lubrizol’s SZ5 and (b) after
ppm sulphur target) as previously formance expected from the catalyst activation with a conventional sul-
presented in Figure 5. In pseudo (independently of the sulphiding phiding agent. For each of the three
first order kinetics, the natural log- agent used for the activation) when catalysts, results indicated that for
arithm of the rate constant is line- it is operating in an ULSD produc- making products with <20 wtppm

20 Catalysis 2019 www.eptq.com

sulphur, sulphiding with SZ54 Go™ Catalyst sulphiding, www.eurecat.com/
delivered the same level of HDS as catalyst-activation.php
sulphiding with DMDS. 8 Jia J, Maesen T, Krenzke D, 2011,
For achieving 10 wtppm sulphur, Hydrocracking pretreat catalyst development,
there were no differences in HDS Advanced Refining Technologies Catalgram®,
www.eurecat.com/catalyst-activation.php
capacity between catalysts activated
9 Magnus P J, Poels E K, Moulijn J A,
with the two sulphiding agents
Temperature programmed sulphiding of
considering the experimental error commercial cobalt oxide – molybdenum oxide
(approximately ±1°C with a confi- (CoO-MoO3)/alumina catalysts, Ind. Eng.
dence level of 95%). Chem. Res., 32, 1993, 1818-1821.
In addition to product sulphur, 10 Moonen R H W (Avantium), World Patent
other important performance indi- 2012047095A1, 2012. Moonen R H W
cators were evaluated: product (Avantium), US Patent 20160121291A1,
nitrogen, hydrogen consumption, 2016. Smit M, Gruter G J M (Avantium), US
liquid product density, and light Patent 7997297B2, 2011. Van den Brink P J,
end yields. In each case, results Bracht M, Harji B H (Avantium), World Patent
2002092219A1, 2002. de Ruiter R R, Bracht
confirmed that SZ54 can be used in
M, Gruter G J M (Avantium), European Patent
commercial applications as a sub-
2263790A3, 2011.
stitute for DMDS without impair- 11 Moonen R, Alles J, Ras E-j, Harvey
ing the overall performance of the C, Moulijn J A, Performance testing of
tested catalysts. All catalysts sup- hydrodesulphurization catalysts using a single-
pliers participating in this study pellet-string reactor, Chem. Eng. Technol.,
acknowledged the results, thereby 40(11), 2017, 2025–2034.
validating the commercial relevance
of the study.
Some aspects of this research Tiago Vilela leads the Refinery Catalyst Testing
(RCT) global services with Avantium and is
may lead to new developments in
accountable for the overall performance of
hydroprocessing catalyst sulphid- the business line. He works with the internal
ing procedures. The difference in project team, marketing staff, and other
activation energies for catalysts sul- managers to increase sales opportunities and
phided with different additives is improve project workflow. With more than 16
unexpected and may lead the way years’ experience in the refining industry, he
to improved sulphiding technology. has advised on numerous projects across the
globe, helping clients to improve their project,
turnaround and operational readiness. He
Flowrence is a trademark of Avantium.
holds a master’s degree in chemical engineering
from the University of Aveiro, Portugal and a
professional doctorate in engineering degree
References from Delft University of Technology, The
1 Lubrizol Corporation is a Berkshire Netherlands.
Hathaway company providing complex
specialty chemicals to optimise the quality, José Castro is a Project Leader with Avantium,
performance and value of our customers’ specialising in hydroprocessing and with
products while reducing their environmental 17 years’ experience in hydrotreating and
impact. hydrocracking technologies and catalysts
2 Avantium Chemicals B.V. is a leading evaluation. He has participated in more
technology company specialised in the than 50 catalyst and technology evaluation
area of advanced catalytic research, with projects using conventional pilot plants and
groundbreaking innovation as the primary goal. parallel testing units, and holds a master
of science degree in advanced chemical
It is a leader high throughput technology for
engineering from Imperial College London
catalyst and process development.
and a bachelor of science degree in chemical
3 Topsoe H, Clausen B, Massoth F, 1996,
engineering from Universidad Central de
Hydrotreating Catalysis, Springer: Berlin.
Venezuela.
4 Albemarle web page, 2018, Hydrotreating,
www.albemarle.com/businesses/refining- Hendrik Dathe is Director of Research
s o l u t i o n s / hy d ro p ro c e s s i n g - c a t a ly s t s / Services with Avantium. In addition to being
hydrotreating responsible for all third party research in the
5 Roberts C D, Improve sulphiding of company’s catalysis business, he is also an
hydroprocessing catalysts, Hydrocarbon expert in the application of enhanced/high
Processing, Sept 2008, 133-135. throughput experimentation in catalyst R&D.
6 Criterion web page, 2018, Catalyst services, He holds a diploma in chemistry from the
www.criterioncatalysts.com/products/ University of Leipzig, Germany and a PhD in
support-and-catalyst-services.html exhaust gas catalyst development from the
7 Eurecat web page, 2018, Totsucat® Load & Technische Universität München, Germany.

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