Coker Naphtha Hydroprocessing Catalysts

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Topsøe Refinery Catalysts

Coker Naphtha Hydroprocessing Catalysts

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Coker Naphthas

In hydroprocessing of coker naphtha feedstocks from delayed coking, silica poisoning of catalysts
often presents a severe problem. The catalyst run length will often be dictated by the amount of
silicon entering with the coker feedstock and by the silica tolerance of the selected catalyst system.
A fundamental understanding of the deposition of silicon and the reaction steps involved has
enabled Topsøe to develop a range of coker naphtha hydroprocessing catalysts with unmatched
silicon pick-up capacities.

Hydroprocessing of Coker Naphthas

Coker naphthas, as well as other coker products, contain
much more sulphur, nitrogen, olefins and aromatic com-
pounds than the straight-run products, increasing the
demand on the hydroprocessing catalyst.
The delayed coker is often used for upgrading of
residual oils. However, products from the delayed coker
add to the processing difficulties encountered in down-
stream hydrotreaters due to the presence of silicon. The
residue from silicone oils used to prevent foaming in
coker drums is largely distilled in the naphtha range and
will cause catalyst deactivation in downstream hydro-
treaters. However, the silicon will also be present in the
diesel and VGO cuts from the coker, although in lower
concentrations than in the naphtha fraction.
Furthermore, coker naphtha feedstocks and other
thermally cracked feedstocks are very rich in diolefins,
which tend to polymerise, which may result in unit pres-
sure drop build-up without the proper use of a graded
bed system.
Topsøe Coker Naphtha Catalysts
Since the operation of each naphtha hydrotreater is
slightly different, the catalyst loading must be tailored
to meet the objectives of each unit.
Based on fundamental knowledge about silicon depo-
sition, Topsøe finds that the best catalyst for a coker
naphtha unit has the following properties:
G A high surface area per reactor volume
G A medium metal loading (NiMo)
G A small particle size (1/20”)
G An active alumina surface
A NiMo catalyst is the best choice for processing of
coker naphtha. Topsøe currently offers three different
catalysts, which are all very effective in treating silicon-
containing feedstocks.
TK-431 is a high surface area catalyst for desulphurisa-
tion of coker naphthas with a moderate to high silicon
content. The metal loading of TK-431 gives this catalyst
a high HDS and a high HDN activity. The pure alumina
carrier used for preparation of TK-431 ensures that this
catalyst has a very high density and a higher surface
area compared with other commercially available coker
naphtha catalysts. As a result, TK-431 has a very high
surface area per reactor volume, which results in a very
high silicon pick-up capacity and, thus, a prolonged cycle
length.

TK-431 TK-437 TK-439

HDS activity High Medium Inactive
Relative metals loading 1.0 0.3 0
Relative silicon pick-up capacity 1.0 1.1 1.3
Application (catalyst) Main bed Guard bed (diolefin) Guard bed

Table 1. The features of Topsøe’s TK-400 series of coker naphtha catalysts.

Haldor Topsøe A/S 2

TK-437 is a very high surface area catalyst for silicon
pick-up and desulphurisation of coker naphtha feedstock.
This catalyst has a low HDS activity and should be used in
combination with TK-431 as a guard catalyst. TK-437 has
the same high surface area per volume as TK-431, but
due to a lower metals loading, the silicon pick-up capacity
is even higher than that of TK-431 on a volume basis.
TK-437 is also our recommended catalyst for diolefin
saturation. Diolefin hydrotreating is best carried out in a
separate guard reactor operating at low operating tem-
perature (350–425°F).
TK-439 has the highest silicon pick-up capacity of all the
TK-400 series catalysts. This catalyst is used as a guard
bed catalyst in units with severe silicon contamination.
TK-439 does not contain any metals and should there-
fore be used in combination with TK-437 and/or TK-431 if
desulphurisation and denitrifications are also required.
The catalyst system should be designed with an opti-
mised graded bed system to minimise pressure drop on
top of a combination of TK-431, TK-437 and TK-439,
which will result in a significantly longer cycle length of
any coker naphtha unit compared with operation on
other typical naphtha hydrotreating catalysts. Table 1
summarises the features of Topsøe’s TK-400 series of
coker naphtha catalysts.
Objectives
The catalytic reformer and its associated naphtha hydro-
treater are found in every modern refinery today. The
content of sulphur, nitrogen and silicon in the reformer
feed is required to be very low, normally below 0.5 ppm.
This requirement can be met without difficulty when the
naphtha hydrofiner processes straight-run feeds while
achieving long cycle lengths. Hydroprocessing of coker
naphthas requires that the catalyst has a very high silicon
capacity since silicon deposition typically determines the
cycle length.

Figure 1. The antifoaming agent PDMS added to the CH3 CH3 CH3 CH3 CH3 CH3
coker is converted into smaller fragments mainly
distilled in the naphtha range at temperatures H3C Si O Si O Si Si O Si O Si CH3
above 450°C. A typical fragment found in the coker CH3 CH3 CH3 CH3 CH3 CH3
naphtha is hexamethyltricyclosiloxane. The silicone
fragments are converted into modified silica gels Decomposition
B
and adsorbed on the catalyst surface. This change in the coker unit
in catalyst surface structure caused by the silica is
associated with the rapid irreversible loss of catalytic
activity observed during hydrotreating of coker
naphtha. The silica gel on the catalyst surface has H3C CH3
been shown to consist primarily of SiO2, Si(OSi)4,
Si
Si(OSi)3OH and various methylated forms: = =SiCH3, O O
=Si(CH3)2. The deposition of silica is a catalysed re- H3C CH3
action, which is moderately diffusion limited. The Si Si
catalytically active sites are known to be surface O
H3C CH3
alumina OH sites.
The adsorbed silica forms a highly dispersed layer
on the catalyst surface. The amount of silica uptake
is therefore related to the surface area of the cata-
lyst. Higher surface area catalysts will give higher
silica uptake provided the catalysts have the same
nickel and molybdenum loading.

Catalysts for All Applications

3 Haldor Topsøe A/S
 Topsøe hydroprocessing catalysts have been developed
in-house and are manufactured in Topsøe plants.
Removal of Diolefins
Formation of diolefins is a result of high-temperature
conversion reactions. Diolefins easily polymerise at nor-
mal hydrotreating temperature conditions, and the poly-
mers often foul the reactor causing pressure drop build-
up. These compounds must therefore be removed
before normal hydrotreating at rather low temperatures
of 175–220°C (350–425°F). Commercially, the naphtha is
often treated in two consecutive reactors: the diolefin
reactor and the main reactor. The diolefin reactor is
used to reduce the diolefins and to trap some of the sili-
con. The main reactor catalyst hydrotreats the olefins,
organic sulphur and nitrogen compounds, and picks up
the remaining silicon.
Origin of Silicon
The origin of the silica deposits can be traced back to the
silicone oil added to the heavy residue feed in the delayed
coker. Because of gas formation, silicone oil (polydimet-
hylsiloxane, PDMS) is usually added to the coker drums
to suppress foaming. This silicone oil is usually cracked
or broken down in the coker to silicone oil fragments
(see Figure 1). These fragments are mainly distilled into
the naphtha range and are sent to a hydrotreater along
with the coker naphtha. Typically, 70–80% of the silicon
100
90
80
Activity Relative to Fresh (%)
70
60
50
40
HDN
30
20
10
0
0 10
% SiO2 on Catalyst
Figure 2. The effect of silica (SiO2) deposition on the catalyst activity.
ends up in the coker naphtha, and the remaining silicon
ends up in the diesel and VGO fractions.
Silica’s Impact on Catalyst Activity
Deposition of relatively large amounts of silica and small
amounts of carbon takes place on the catalyst during
coker naphtha hydroprocessing. The effect of silica (SiO2)
deposition on the catalyst activity has been studied at
Topsøe’s research facilities on commercially aged cata-
lyst samples. The results of this work can be seen in
Figure 2. The most profound effect is seen for the HDN
activity. At a level of 20 wt% SiO2 (10% Si) on the cata-
lyst, the HDS activity of most catalysts was reduced by
only 30%, whereas the HDN activity was reduced by
90%. Since the denitrogenation is more affected by sili-
con deposition than the desulphurisation, Topsøe recom-
mends that the denitrogenation activity of the catalyst
is followed during the run to define the silicon contami-
nation and to better determine the expected end-of-run.
When the denitrogenation activity becomes unaccept-
able, the silicon breakthrough may be imminent, even
though the desulphurisation is still satisfactory.
Another unfortunate effect of silica deposition is that
the silica makes the catalyst unregenerable, because the
silica is adsorped on the entire catalyst surface, resulting
HDS
20 30 40
Haldor Topsøe A/S 4
in irreversible loss of surface area, pore volume and
active sites.
The silica species are distributed on the catalyst sur-

Si content
face in the same way as the coke is deposited. This
means that silica does not act as a catalyst poison by
bonding to a metal site but by blocking the catalyst pore
system and accessing the active metal sites. After a cer-
tain accumulation of silica on the catalyst surface, a
rapid catalyst deactivation will occur.
The silicon competes with the catalytically active met-

als for the same sites on the catalyst carrier. Conse-
quently, a catalyst with a low metals loading will have a
higher silica uptake than a catalyst with a higher metals
loading as seen by Topsøe for TK-437 and TK-439. The
TK-439 without metals is in fact the most efficient sili-
con trap of the TK-400 series catalyst.
Operating Conditions
Topsøe has determined that the silicon pick-up is not de-
pendent on the unit pressure, but very dependent on
the operating temperature. At a higher operating tem-
perature, the silicon pick-up is higher. Figure 3 shows the
silicon uptake with temperature. There is no indication
of the fact that the curve has reached its maximum. For
maximum Si uptake, Topsøe thus recommends opera-
tion at the highest possible temperature.
Diffusion of Silicon Species
The deposition of silica on naphtha catalysts is a fast re-
≈
Surface Center Surface
Catalyst 1 Catalyst 2 Catalyst 3 Catalyst 4
Figure 4. Silicon profiles for 1/20” catalyst pellets.
action, which leads to diffusional limitations in catalysts
larger than 1/20” in diameter. For 1/20” pellets, a micro-
probe analysis showed that the silica-contaminated hy-
drotreating pellets from all levels of a reactor had a uni-
form distribution of silica throughout the entire catalyst
pellet diameter (Figure 4).
The same analyses carried out on larger pellets (›1/20”)
showed that the silica was not deposited uniformly
through the entire pellet diameter, but had a higher ac-
cumulation of silica toward the outside of the pellets.
Depending on the process conditions in the coker
naphtha unit, the silicon deposition appears to be some-
what diffusion limited in catalyst pellets larger than
1/20”.

14
TK-439
12
TK-437
TK-431
% Si on spent catalyst

10

0
0 10 20 30 40

Temperature

Figure 3. Silicon uptake with temperature.

5 Haldor Topsøe A/S

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The information and recommendations

have been prepared by Topsøe special-
ists having a thorough knowledge of
the catalysts. However, any operation
instructions should be considered to
be of a general nature and we cannot
assume any liability for upsets or dam-
age of the customer’s plants or person-
nel. Nothing herein is to be construed
as recommending any practice or any
product in violation of any patent, law
or regulation.