Guarding against contaminants

Analysing spent hydroprocessing catalyst underpins the development of guard

bed catalysts to counter contaminants

Michael SCHMIDT Haldor Topsoe A/S

Henrik Rasmussen Haldor Topsoe Inc

A
very important parameter
for the cycle length of a S Sulphur
Vanadium
hydroprocessing unit is
Nickel
the deactivation rate of the Aromatic rings S
installed catalyst. The deactiva- Naphthenic rings
tion of a hydrotreating catalyst
S S
can be coke induced and
contaminant induced. Coke
S
deposition is to a large extent S
controlled, but also dictated, by S
the unit operating regime
S
(temperature, hydrogen availa- S S

bility, residence time and partial S S

pressure of hydrogen). This will
normally cover most middle S S S
distillate units making ULSD or
S
lighter products. However, in S
S
units processing heavier feed-
S
stocks like vacuum gas oil
(VGO), heavy coker gas oil
(HCGO), deasphalted oil (DAO),
or even heavier cuts, the refinery Figure 1 Large porphyrin-like asphaltene molecule
normally faces a dual type deac-
tivation. The coking reactions here are even Topsoe researchers have within the past few
more significant because the feedstock is heavy years analysed and characterised a huge number
and contains lots of aromatic coke precursors in of spent catalysts retrieved from industrial
the high boiling fraction. But heavy feedstocks hydrotreater units operating on heavy feedstocks
will often also contain a significant amount of like VGO and HCGO. This characterisation work
heavy metals and other contaminants. In tries to understand how these contaminants are
particular, this includes nickel, vanadium, iron, deposited to help us develop more effective
silicon, arsenic, phosphorus, calcium and guard bed catalysts.
sodium. These contaminants are present in
processed feedstocks at ppm or even ppb levels, Contaminants to deal with
but the effect is significant. Following a non-re- In general, the heavier the hydrocarbon cut the
versible pathway, heavy metals will be deposited higher the content of contaminants. In a feed
on active catalyst following different mecha- stream such as VGO, DAO and HCGO, metals
nisms. The outcome is that activity is lost contamination is therefore mainly an issue for
permanently and will thus not even be regained FCC pretreaters, hydrocracker pretreaters and
during catalyst regeneration. lube units.

www.digitalrefining.com/article/1001244 Catalysis 2016 1

 Vanadium and nickel are mainly found in
large, porphyrin-like structures (asphaltenes) in
crude oil (see Figure 1). Generally, the metallic
species of the crude are concentrated in the resid
portion, but some organometallic species are
present in the lower boiling ranges with a boiling
point above 660°F (350°C).
Introduction of feeds containing vanadium,
nickel or iron (such as atmospheric tower
bottoms) into VGO hydrotreating could have
severe consequences in terms of cycle length.
The relatively high space velocity of these units
(compared to resid hydrotreating) could result in
metal migration into the active, main bed cata-
lyst. To overcome this problem, a highly active
demetallation catalyst with a high metal pick-up
capacity must be installed on top of the main
catalyst bed. Topsoe has commercialised
specially designed VGO demet catalysts desig-
nated TK-453 and TK-455 MultiTrap.
The large molecules containing these metals
require catalyst shapes with a high surface to
volume ratio to remove these metals efficiently.
Iron will mainly deposit on the catalyst surface,
whereas nickel and vanadium will deposit inside
the catalyst pore structure due to the very large
average pore sizes of TK-453 and TK-455.
Arsenic is a true catalyst poison as it will
chemically react with active catalytic sites, for
instance transforming the catalyst’s nickel and
cobalt into NiAs or CoAs. Poisoned sites will not
be reactivated during regeneration, and even
small amounts on the catalyst will affect catalyst
activity in a critical way. Fortunately, the
concentration of arsenic is in the ppb range and
can be effectively dealt with by utilising Topsoe’s
high capacity arsenic traps TK-49 as an extru-
date, and TK-45 and TK-41 in a ring shape.
Silicon found in oil fractions originates from
Si-containing anti-foam additives used in coker
units, as well as from the use of chemicals intro-
duced during oil transport and tertiary oil
recovery. Silicon reacts with the surface of the
catalyst and forms a silica gel, hindering access
to the active catalytic sites and thereby deacti-
vating the catalyst. Silicon penetrates into the
pore system of the catalysts, and deactivation is
proportional to the concentration of silicon on
the catalyst.
Haldor Topsoe’s TK-400 series catalysts for
naphtha and TK-453 for heavier fractions provide
the highest silicon pick-up on a volume basis.
2 Catalysis 2016
Phosphorus species are rarely found in typical
crudes; however, some opportunity crudes (and,
in particular, renewable feeds) often contain
significant amounts of phosphorus. Furthermore,
phosphorus containing anti-corrosion additives
can be found in diesel and VGO fractions.
Phosphorus compounds are decomposed in the
hydrotreater, and the phosphates react with the
alumina support (much like silicon), forming very
stable aluminium phosphates. Accumulated
amounts of phosphates will reduce accessibility to
the active sites of hydrotreating catalysts and
lower the activity accordingly. Phosphorus
compounds are often found to originate from
injection of corrosion inhibitors in the form of
thiophosphorus compounds like thiophosphate
esters, thiophosphites and tributyl phosphate.
Handling of organic phosphorus compounds
in the VGO being fed to FCC pretreaters or
hydrocracker pretreaters is a major challenge in
some refineries. The phosphorus quickly deacti-
vates the conventional catalyst and reduces cycle
length dramatically. Topsoe has developed
specific guard bed catalysts, TK-31 and TK-455
MultiTrap, to effectively protect the main cata-
lyst. These guard catalysts, with proprietary
properties and composition, will be able to
prolong the cycle length of the unit.
The main source of sodium in a FCC or hydro-
cracker pretreat feed is normally poorly desalted
crudes. This type of inorganic sodium will not
easily enter the catalyst’s pore system. Sodium
will therefore tend to deposit around the exterior
of the catalyst, forming a solid crust between
catalyst pellets, which will harm activity and
cause pressure drop issues.
We should not forget to mention inorganic
iron, which is a very common contaminant. Iron
rust originates from corrosion of upstream
equipment and may consist of everything from
large flakes to the smallest particle tank rust.
Large particle rust is known to be easily trapped
in filters, scale catchers and high void catalytic
materials. However, 5-10 micron inorganic iron
particles are very hard to handle as they will
pass feed filters and, without a proper graded
bed system, enter the catalyst bed. Inorganic
iron will also preferentially deposit in the outer
surface of the catalyst, unless a very large pore
demet catalyst is utilised as a guard catalyst, and
will eventually lead to increasing pressure drop.
To handle inorganic iron, Haldor Topsoe intro-
www.digitalrefining.com/article/1001244
duced themacroporous Demetallisation functionality
particulate trap TK-25 TopTrap (HDM) in a gas oil hydrotreater
a number of years ago and it has is a function of pressure, temper-
proven to be a leading trap ature, residence time (LHSV),
material. catalyst and feed. The catalyst
The company recently system selected is a key factor in
launched an improved particu- determining the cycle length. It
late trap, designated TK-26 is not only important to install
TopTrap, with an optimised the proper HDM catalysts but
daisy shape with three axial also a main bed catalyst that has
holes to provide about 20x Figure 2 Macroporous particulate both a high capacity and toler-
higher pick-up capacity as trap TK-26 TopTrap ance for metals.
compared to TK-25 TopTrap. The metal capacity of a hydro-
TK-26 TopTrap is designed with a 61% particle treating catalyst is mainly determined by the
void fraction as well as a large internal pore catalyst’s porosity. However, the rate of metal
volume and macro pores Larger sized inorganic removal is a catalytic reaction and is therefore
contaminants deposit in the spaces between very much dependent on catalyst activity and
traps; fines or smaller sized materials enter the reactor operating temperature. Based on experi-
pore system and are trapped within the structure ence, it is advisable to have reactor temperatures
of the particle itself (see Figure 2). Theinternal above 600°F (315°C) to ensure that enough
particle void of TK-25 TopTrap is 25%, so that the demetallisation takes place. The severity of the
total void in this product is greater than 85%. feed is also an important factor. The actual metal
More exotic metals like calcium, zinc and pick-up for a catalyst is dependent on all of the
magnesium are also observed in some units. above factors.
These can all originate from different additives Haldor Topsoe’s demet catalysts show very
but are also occasionally found in porphyrin high metals pick-ups, with as much as 40 wt% of
structures in crude. These contaminants are nickel plus vanadium pick-up in FCC pre-treat
quite common in units upgrading spent lube oils service and over 20 wt% each of both silicon and
to new base lubes stocks and can be a challenge. phosphorus. This high level of capacity of demet
They are harmful to the main bed catalyst catalyst will protect the main bed catalyst and
because they tend to stick to the surface of the allow for longer run lengths.
catalyst, thereby preventing access to the pore Our main bed catalysts, BRIM and HyBRIM,
system. Table 1 summarises the mechanisms of show a high level of both capacity and tolerance
contamination. for metals. In FCC pre-treat services, these cata-
The importance of utilising specialised graded lysts have shown as much as 25 wt% of nickel,
bed catalysts and guard catalysts designed to vanadium and iron. Designed with an optimum
handle these many poisons with different depo- combination of pore diameter, pore volume and
sition mechanism cannot be overstated. The ‘one surface area, the catalysts have also shown pick-
size fits all‘ approach will simply not provide the ups as high as 20 wt% of silicon and phosphorus.
refiner with an optimised cata-
lyst loading for proper Contaminants overview
protection of the main bed cata-
lyst and the cycle length will be Contaminant Ni/V Fe As Fe Si P Na
Origin Crude Crude Crude Corrosion Additives Additives Salt
reduced. Haldor Topsoe has Typical VGO feed 1-5 1-3 50-250 0-3 0-3 0-2 0-2
fine-tuned its catalyst portfolio concentration wtppm wtppm wtppb wtppm wtppm wtppm wtppm
Contamination Precipitation Precipitation Titrating Reducing Absorbed Coating
to provide proper main bed mechanism on as sulphides.as sulphides. active void to catalyst of
protection by constantly adding main bed Pore mouth Pore mouth sites resulting surface area. catalyst
new and improved graded bed catalyst plugging plugging forming in pressure Co-reaction exterior
arsenides. drop with P
products. This is illustrated in Real poisoning
Figure 3, which expresses 23 Severity + + +++ + +(+) +++ ++
graded bed products as a func-
tion of size vs catalytic activity. Table 1

www.digitalrefining.com/article/1001244 Catalysis 2016 3

 hydrotreating units every year,
Products and we analyse the contents after
11/2in TK-15 the cycle to continuously opti-
mise the catalyst formulation for
5/ in
8 TK-10 maximum pick-up of the
1/ in TK-26 contaminants mentioned here.
2
TopTrap
Our research laboratories are
Size

3/ in equipped with a wide range of

16 TK-30 TK-709 TK-710 TK-45

1/ in
analytical tools for characteris-
TK-30 TK-335 TK-437 TK-337 TK-41 TK-831
8
ing spent catalysts. ICP-MS,
1/ in QL
10
TK-455
TK-31 TK-339 Multi- TK-341 TK-743 TK-453
X-ray fluorescence, X-ray
Trap diffraction and state-of-the-art
1/ in QL TK-340 TK-49 microscopy are within the range
15
of possibilities.
Activity The first thing in the toolbox
is always to characterise the
Figure 3 Haldor Topsoe’s graded bed products spent catalyst using a precise
bulk analysis method. An exact
Retrieving spent catalyst samples quantification of what is present in the sample is
It is essential to have access to relevant and required. The most efficient method to apply for
representative spent catalyst samples if a detailed this purpose is
understanding of contamination type, degree and inductive coupled plasma mass spectrometry
profile is to be obtained. Because the contamina- (ICP-MS).
tion process is difficult to simulate in a realistic Scanning electron microscope (SEM) and elec-
manner in lab-scale pilot units, almost all devel- tron micro probe analyser (EMPA) are tools
opment work for making new, improved guard used to determine the chemical composition in
catalysts relies on retrieving industrially aged localised areas of solid materials. The method is
spent catalysts. One option is to sample catalyst ideal for a combination of structural and chemi-
while the industrial reactor is being unloaded. cal information. An electron beam interacts with
This obviously gives valuable information about the sample and produces electrons both for
the contamination profile and illuminates how imaging and characteristic X-rays. Both the
well certain contaminants migrate through the energy and the wave length of the X-rays can be
different catalyst layers. The best way to get good detected.
samples is to unload the catalyst by vacuuming.
However, if the catalyst is being dumped through The strength of canisters and spent catalyst
a bottom dump chute it is not possible to identify analyses
the exact position of the catalyst that is being Topsoe installed canisters in a hydrotreater
sampled. The catalyst unloaded by gravity designed to process and upgrade spent lube oils
through a dump tube will funnel out like grains to base oils and group 2+ lubes. Spent lube oil
emptying from a silo. Alternatively, we recom- contains large amounts of contaminants and
mend using Petroval’s sampling method called additives, such as zinc, magnesium, calcium and,
Probacat, which will drill down through the bed in particular, phosphorus and silicon. All of these
and a set of perfect core samples of the bed is contaminants deposit on catalysts, causing signifi-
collected. cant loss of activity. Two canisters were installed
The other option is to have catalyst test baskets in the top of the reactor with catalysts having
or canisters installed in a known location within different properties (pore volume, pore size,
the reactor during the entire cycle. The canister surface area and active metal content). Besides
will hold several catalysts in different compart- the canisters, catalyst samples were also obtained
ments, and each catalyst within the canister is from the unloading of the three reactors. Some of
exposed to practically the same type and amount the unloaded catalyst samples had been in opera-
of contaminants. In collaboration with clients, tion for one cycle and other samples had been in
Topsoe installs 10-20 test canisters in various the reactor for two cycles.

4 Catalysis 2016 www.digitalrefining.com/article/1001244

Analysis by ICP-MS
The spent catalysts unloaded Largest pore size Large pore size
Si

Pick-up (fresh catalyst basis)

Highest pore volume High pore volume
from the reactors were analysed P Low activity Medium activity
using ICP-MS in order to quan-
tify the bulk amounts of
phosphorus and silicon in Medium pore size
particular. This analysis Medium pore volume
High activity
confirmed that the catalysts
indeed were heavily contami-
nated. The numbers also
confirmed the theory that cata-
lysts with a high pore volume
and large open pores could trap TK-562 Brim TK-455 MultiTrap TK-743
most phosphorus and silicon.
Figures 4 and 5 illustrate how Figure 4 Bulk analyses for phosphorus and silicon: canister test (ICP-MS)
three different catalysts from
the canister picked up different
Unit B reactor results: spent lube HDT
amounts of phosphorus and sili- Gradient from top to bottom
con, reflecting the difference in
Reactor top Reactor bottom
porosity and activity.
Pick-up (fresh catalyst basis)

Si
2 cycles
Analysis by SEM and EDS P
Now it was time to apply the
1 cycle
SEM technique to map and
quantify exactly where the 1 cycle
contaminants were present.
Figures 6 to 8 show the quantita-
tive cross-section analyses of
TK-562 BRIM, TK-831 and
TK-743 using the SEM/EDS
technique. These catalysts were
all grabbed from different loca- TK-831,1/8in R TK-743,1/10in QL TK-562,1/16in TL
tions in the reactor and represent
a bulk catalyst, a graded bed Figure 5 Bulk analyses for Si and P: samples from the catalyst bed (ICP-MS)
catalyst and an effective HDM
catalyst. Hence, the last two mentioned have the within the catalyst pellet than was the case for
biggest pore systems and the largest pores. TK-562 BRIM. The crust itself is again very rich
A firm crust of phosphorus is seen on the in phosphorus, silicon and the other
surface of the main bed catalyst pellet. The phos- contaminants.
phorus content in the crust exceeds 15 wt% and The data shows a good correlation between the
silicon is around 10 wt%. In fact, the crust catalyst’s porosity and pore size and its ability to
appears to be a complex matrix of the impurities allow phosphorus and silicon compounds to
of the spent lube oil as it also contains high enter the catalyst pore system. This data as well
amounts of calcium, magnesium and zinc. The as dozens of other similar canister studies has
two measurements made within the catalyst pellet enabled Haldor Topsoe to generate optimised
show a steep drop in the phosphorus content, catalysts designed to pick up the specific poisons
whereas silicon is fairly constant at all points. causing issues in each individual hydrotreating
Looking at the TK-831 and TK-743 samples, unit, resulting in a better performance and cycle
there is a significant difference. While they also length. The graded bed system needs to be
have a crust layer surrounding them, the crust is designed for each unit to effectively eliminate
thinner and, more importantly, the phosphorus unit constraints.
species are found in much higher concentrations

www.digitalrefining.com/article/1001244 Catalysis 2016 5

 OK NaK MgK AsL AlK SiK PK MoL SK CaK VK FeK CoK NiK ZnK
1 41.6 3.6 1.4 0.9 <0.5 6.0 15.7 <0.5 6.2 14.9 0.0 1.4 <0.5 0.0 7.0
2 39.9 3.7 1.3 1.0 <0.5 1.3 24.5 <0.5 2.3 17.1 0.0 1.2 <0.5 0.0 6.1
3 44.2 2.7 1.1 0.6 <0.5 10.2 16.9 <0.5 4.9 11.7 0.0 0.9 0.5 0.0 5.5
Catalyst
4 44.2 2.2 1.5 <0.5 <0.5 9.7 16.5 <0.5 4.6 12.4 0.0 1.2 0.6 0.0 6.0
5 51.2 2.9 1.0 <0.5 <0.5 10.2 15.5 <0.5 2.4 12.6 0.0 1.0 <0.5 0.0 1.8
6 46.6 1.3 <0.5 <0.5 14.7 8.9 9.8 4.3 5.0 5.0 0.0 0.6 1.3 0.0 1.0
Crust
7 44.6 <0.5 <0.5 <0.5 24.0 10.5 5.0 5.9 6.7 <0.5 0.0 0.2 2.0 0.0 0.6

Catalyst 8 42.6 <0.5 <0.5 <0.5 26.7 10.0 2.5 6.3 7.7 <0.5 0.0 0.2 2.4 0.0 0.6
wt%

Figure 6 EDS analysis of a cross-section of TK-562 BRIM

OK NaK MgK AsL AlK SiK PK MoL SK CaK VK FeK CoK NiK ZnK
1 33.0 2.8 1.0 0.9 0.7 10.9 23.4 3.7 0.7 25.7 0.0 2.3 0.0 0.5 5.9
Catalyst 2 51.7 5.2 1.0 <0.5 <0.5 3.5 18.0 <0.5 2.2 8.9 0.0 0.7 0.0 0.6 2.4

3 30.5 0.8 <0.5 <0.5 23.5 4.1 14.4 0.7 3.0 <0.5 0.0 <0.5 0.0 1.4 <0.5

Crust 4 42.2 <0.5 <0.5 <0.5 26.1 4.7 18.3 2.7 2.5 <0.5 0.0 <0.5 0.0 1.3 0.7

5 44.4 <0.5 <0.5 <0.5 27.4 5.2 14.9 2.1 2.4 <0.5 0.0 <0.5 0.0 1.5 0.6

6 52.9 <0.5 <0.5 <0.5 24.0 5.8 11.5 1.6 1.8 <0.5 0.0 <0.5 0.0 1.1 <0.5
Catalyst
wt%

Figure 7 EDS analysis of a cross-section of TK-831 (ring shape)

OK NaK MgK AsL AlK SiK PK MoL SK CaK VK FeK CoK NiK ZnK
1 33.7 3,7 1.0 0.0 0.7 5.2 14.9 0.0 8.6 14.5 0.5 1.2 0.0 0.5 14.2
Catalyst 2 48.0 4.4 0.9 0.5 2.3 4.9 12.8 0.0 6.6 10.8 <0.5 0.7 0.0 <0.5 7.3

3 47.7 1.5 <0.5 <0.5 21.4 4.3 10.5 2.7 5.0 2.7 <0.5 0.6 0.0 1.7 0.8

Crust 4 51.2 <0.5 <0.5 <0.5 25.3 4.0 8.4 3.6 4.3 <0.5 <0.5 <0.5 0.0 1.8 <0.5

5 48.7 <0.5 <0.5 <0.5 29.3 4.5 7.3 2.7 4.2 <0.5 <0.5 <0.5 0.0 1.8 0.6

6 46.0 <0.5 <0.5 <0.5 32.9 5.1 6.4 3.2 4.0 <0.5 <0.5 <0.5 0.0 1.5 <0.5

Catalyst wt%

Figure 8 EDS analysis of a cross-section of TK-743 (HDM catalyst)

Michael T Schmidt is Product Manager with Haldor Topsoe,

responsible for the development and quality of Topsoe’s FCC LINKS
pretreat and hydrocracking pretreat catalysts. He holds a degree
in chemical engineering from the Technical University of Denmark. More articles from: Haldor Topsoe
Henrik Rasmussen is Vice President of Catalyst and Technology
More articles from the following categories:
with Haldor Topsoe, responsible for the catalyst and license
Catalysts & Additives Fluid Catalytic Cracking
technology business for the US, Canada, and the Caribbean. He
Precious Metals Recovery
holds a degree in chemical engineering from the University of
Copenhagen.

6 Catalysis 2016 www.digitalrefining.com/article/1001244