Coker naphtha hydrotreating

Highly exothermic olefins saturation and silica contamination can occur when
hydrotreating coker naphtha
Rasmus Breivik and Rasmus Egebjerg Haldor Topse A/S

n recent years, the application of residue

upgrading technologies has grown in a market
with increasing prices for light sweet crudes
and a decreasing demand for heavy residual fuel
oil. Carbon-rejection technologies such as
delayed cokers have been the preferred choice,
since crude quality declines with increasing
metal content and Conradson carbon residue
(CCR).
Installation of a new coker unit, resulting in an
increase in cracked distillate, poses some additional challenges to downstream hydrotreaters.
This is particularly the case for naphtha hydrotreaters, since the properties of coker naphtha are
very different from those of straight-run (SR)
naphtha.

Coker naphtha contaminants

Typically, coker naphtha contains 1020 times
more sulphur and higher amounts of olefins,
nitrogen and silica than SR naphtha. Target
levels of nitrogen in the reformer feed are around
0.10.5 wtppm to avoid ammonium chloride
deposition. This implies that the coker naphtha
hydrotreater needs to be operated at high severity to meet the required product specifications
on nitrogen. However, it is practically impossible
to increase operating severity with a higher
temperature, since sulphur recombination takes
place at high temperatures.
The origin of the silica can be traced back to
the silicone oil added to the heavy residue feed
to the coker. As a result of gas formation, silicone oil is added to the coker drums to suppress
foaming. Excess quantities of silicone oil will
crack or decompose to form modified silica gels
and fragments. These are mostly distilled in the
naphtha range and carried to the downstream
hydrotreaters together with coker naphtha.

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Unfortunately, silica poisoning of the catalyst

in the downstream hydrotreaters reduces HDN
activity and results in large catalyst volumes
being required to ensure simultaneous removal
of nitrogen and silica. The required space velocity to match the turnaround schedule of the
reformer/coker unit will often be below 0.2hr-1
when using standard hydrotreating technology
and catalyst.
Another important consideration for coker
naphtha hydrotreating is control of the temperature increase from olefins saturation, since this
reaction takes place readily and is highly exothermic. When olefin saturation is not properly
controlled, this may lead to a premature shutdown, as excessive coke formation will take place
due to gum formation/polymerisation in the top
layer of the catalyst bed. In the future, it is
expected that there will be a higher ratio of
cracked components in the refinery slate.
For new grassroots units, a three-reactor layout
is typical. In the first reactor, diolefins are mainly
saturated at low temperature. In the second,
silica is adsorbed on high-surface area catalysts
known as silica guard. Simultaneously, most of
the olefins are saturated, while a relatively large
degree of HDS and a small degree of HDN take
place. Finally, a reactor with high HDS and HDN
activity catalyst ensures the sulphur and nitrogen
specifications are met. Even when operating with
only two reactors, these three steps must be
carried out.

Controlled removal of conjugated olefins

Olefins formation is a result of high-temperature
conversion reactions in the delayed coker. Upon
contact with air, olefins and diolefins may form
gum that complicates the transportation and
processing of coker naphtha. Diolefins and, in

PTQ Q1 2008 1

Selectivity

Selectivity

Conversion

Catalyst B
Catalyst A
Conversion

Figure 1 Selectivity of diolefin saturation reaction

Feed

Feed

660

Product
Product

Figure 2 Bypass silica reactor (left) and lead/lag reactor

system (right)

particular, conjugated diolefins present in coker

naphtha must be saturated in order to stabilise
the feed. The stabilisation takes place in a separate reactor, since the required operating
conditions are quite different from those of the
HDS and HDN reactions. The saturation of
diolefins is a fast reaction and can therefore be
carried out at high LHSVs and at low temperatures. Conjugated diolefins polymerise at normal
hydrotreating conditions, and the polymers cause
fouling of the reactor, resulting in pressure drop
build-up. The polymer formation potential of
coker naphtha is about 300 times the potential
for SR naphtha. A generally accepted way of
controlled saturation of conjugated olefins is to
use a hydrotreating catalyst operated at a low
temperature (160220C) in the presence of
hydrogen.
With the growing market for coker technology,
focus is put on the reliability of the coker unit,

2 PTQ Q1 2008

resulting in more coker units being designed

with ISBL facilities to remove conjugated olefins.
The benefit of making the removal of conjugated
olefins independent of the coker naphtha hydrotreater is the possibility of sending the coker
naphtha directly to storage if the coker naphtha
hydrotreater offers an unforeseen shutdown.
Many units are currently designed independently
of the coker naphtha hydrotreater with oncethrough hydrogen, which facilitates the change
of catalyst on-line to increase coker unit
reliability.
Since the exothermic diolefin reactions produce
large amounts of heat, it is necessary to operate
at low temperatures using a selective catalyst to
control the temperature increase. High selectivity means the catalyst should saturate diolefins
only and not mono-olefins, which might lead to
too high a temperature increase in the reactor.
Topse has carried out studies of catalyst selectivity by processing a model feed containing 1,
3-hexadiene. The diolefin-to-olefin reaction
selectivity was studied as a function of diolefin
conversion, as shown in Figure 1a. As expected,
the selectivity decreased with conversion, since
the two reactions (saturation of 1,3-hexadiene to
hexenes and saturation of hexenes to hexane)
are consecutive.
The effect of pressure was also investigated. In
Figure 1b, the selectivity is shown as a function
of the reactor pressure for two catalysts. At all
conditions, the hexadiene is completely
converted, but the selectivity towards hexane
increases with decreasing pressure. Furthermore,
the two catalysts tested have different selectivity
and slightly different responses to changes in
pressure. This means that even though the saturation reaction is fast, there are a number of
knobs that can be turned to control the reactions
to ensure complete saturation of diolefins and
high selectivity towards olefins are achieved. This

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knowledge is used to optimise the selection of

catalyst and process conditions to maximise the
run length.

Silica removal and olefin saturation

rected to have the fresh catalyst in the lag

position and the partially saturated silica guard
in the lead position. The lead/lag reactor system
is preferred for hydrotreater units processing
high amounts of coker naphtha. This solution
has the advantage that a very high temperature
increase can be allowed across the silica guard
system.
With the lead/lag reactor system, it is possible
to process a larger fraction of coker naphtha
than with the bypass reactor configuration.
Typically, the fraction of coker naphtha is
controlled by recycling part of the product to
dilute the coker naphtha fraction. Allowing a
larger fraction of coker naphtha to be processed
would therefore decrease the actual throughput
of the high-pressure reactor section, reducing
both investment and operating cost. Another
benefit would be the full utilisation of the silica
guard, since a large silica slip can be tolerated to
the lag reactor, ensuring the maximum silica
pick-up in the lead reactor is reached before the
catalyst change-out.
Extensive studies have been conducted to
determine the mechanism of catalyst deactivation when subjected to coker naphtha feedstocks
containing silicon. These studies investigate the
nature of the silicon deposition chemistry and
the effect of silica contamination on HDS and
HDN activity. Silica in coker naphthas originates
from silicone oil added to the heavy residue feed
in upstream processes. Typically, the silicone oil

The simultaneous removal of silica by adsorption

and saturation of olefins requires a proper design
of both the catalyst system and process schemes
to control temperature increases and pressure
drop build-up.
The amount of silicon in coker naphthas is
dependent on the economics of the coker unit.
Typically, a coker naphtha fraction contains
about 5 wt ppm silicon, but silicon contents of
up to 10 wt ppm can be seen on some occasions.
Unfortunately, silica poisoning of the catalyst in
the downstream hydrotreaters reduces the HDN
activity of the catalyst to a large degree.
Typically, when processing feedstocks in the
past with low silica contents, the approach was
to allow the silica to be absorbed on the bulk
catalyst, since only a small amount of catalyst
was required to remove silica. However, with the
increasing amount of coker material to be processed, the content of silica and nitrogen has
increased, and it is nowadays desirable to confine
the silica deposition to the guard material to
allow the use of a high-activity catalyst as a bulk
catalyst. Different configurations can be selected
for the silica reactors, dependent on feedstock
and refinery-specific considerations (Figure 2):
Bypass silica reactor
Lead/lag reactor system.
Typically, the bypass reactor configuPolydimethylsiloxane
ration is selected for hydrotreaters
operating with a low content of coker
CH3
CH3
CH3
CH3
naphtha and a high amount of silica.
.
.
.
.
.
.
.
Si
O
Si
O
Si (CH3)3
The main problem with a bypass reac- (CH3)3 Si O Si O Si
tor is that the heat integration should
CH3
CH3
CH3
CH3
be prepared for switching the temperature increase from the silica guard
CH3
CH3
reactor to the main hydrotreater reacSi
H3C
O
H
C
CH
3
3
tor during catalyst change-out. This
Si
O
Si
limits the fraction of coker naphtha to
CH3
CH
3
be processed with this reactor
O
O
O
Si
CH3
H3C
configuration.
CH3
O
Si
Si
Si
In a lead/lag reactor configuration,
H3C
CH3
CH3
CH3
O
two reactors are connected in series
Hexamethylclotrisiloxane
Octamethylcyclotetrasiloxane
(Figure 2). When the lead reactor is
saturated with silica, the catalyst may
be replaced while still running the unit Figure 3 Structure of silicone oil (PDMS) and typical decomposition
at full capacity. The flow is then redi- products (cyclic siloxanes) present in coker naphthas

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PTQ Q1 2008 3

surface groups SiOH and Si(OH)2

and partly of modified silica gels
with methylated surface species.
The deposition of Si is similar to
the deposition of coke. No chemical bonds to the alumina or metal
sulphides are formed. The deactivation is caused by adsorption
on surface reaction sites reducing
the amount of active sites that
the sulphur and nitrogen species
Temperature, C
Temperature, C
have access to. However, the loss
of activity due to Si is irreversible
Figure 4 Influence of catalyst-specific surface area (left) and operating
and cannot be restored by catatemperature (right) on the Si uptake capacity
lyst regeneration.
The deposition has been shown
is a polydimethylsiloxane (PDMS). At the to be an activated and diffusionally controlled
elevated temperature of the delayed coker, PDMS reaction catalysed by the surface alumina sites.
decomposes, and Topse has identified a homo- This means the silicon uptake capacity is higher
logue series of cyclic siloxanes in coker naphthas, for catalysts with higher specific surface areas
examples
of
which
are
shown
in and that, at higher bed average temperatures,
Figure 3.
the silica capacity of the catalyst will be higher
The amounts of these siloxanes causing the (Figure 4). In order to fully utilise the silica
catalyst deactivation are determined by a quanti- capacity of the guard, it is thus necessary to
tative Si-sensitive GC analysis. Furthermore, the design the heat profile of the entire unit properly
interaction of these siloxane species with the from SOR to EOR.
catalyst surface as well as a characterisation of
The influence of Si deposition on catalyst activspent catalysts have shed light on the deactiva- ity is more pronounced for HDN than for HDS
tion mechanism. The cyclo-siloxanes are quickly (Figure 5), and the HDN activity can thus be
adsorbed on the catalyst surface. A detailed char- followed to track silicon contamination. These
acter-isation of the Si deposits on aged coker findings have implications for catalyst design
naphtha HDT catalysts was carried out by NMR with respect to maximising Si capacity and HDS/
spectroscopy. Si is present in the form of modi- HDN activity. Since the surface alumina sites are
fied silica gels consisting partly of bulk Si02 with responsible for the decomposition of the siloxane
species, a low metal loading and
a high surface area are optimum
for Si uptake. However, low
metal loadings result in a low
HDS/HDN activity. The knowlHDS
edge acquired from fundamental
studies of silicon deposition
chemistry combined with canister tests in industrial coker
HDN
naphtha hydrotreaters has led to
the development of Topse TK431,
TK-437,
and
TK-439
catalysts, allowing an optimum
design of the silicon guard catalyst system. This catalyst series
SiO2 on catalyst, wt%
consists of catalysts with varying
silica capacities and HDS/HDN
Figure 5 Influence of SiO2 deposition on HDS and HDN catalyst activity
activities.
Depending
on
Si capacity of TK-437

Activity relative to fresh, %

Selectivity

Si on spent catalyst, %

Si capacity of TK-431

4 PTQ Q1 2008

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feedstock reactivity and operating conditions, the

correct catalyst system can be selected, maximising cycle length.

Interbed cooling
The combination of high olefin content and the
low-end boiling point of coker naphtha results in
large temperature increases, which are typically
seen across the first catalyst bed. For high
concentrations of olefins, temperature increases
of more than 100C have been observed in
industrial units. The combination of a high
temperature increase and the possibility of
sulphur recombination, which requires a low
temperature, results in a substantial need for
interbed cooling.
In the past, interbed cooling was carried out
by quenching with cold gas or liquid. However,
with increasing energy prices, alternative ways of
cooling need to be considered. Topse recently
developed a new technology utilising the high
temperature increase to improve heat integration
by applying interbed heat exchangers. This new
concept not only improves heat integration, but
also increases catalyst activity, since the treat gas
rate and fugacity can be controlled independently of the required cooling requirements. The
concept has already been applied in the design
of several coker naphtha hydrotreaters.

Grading
The high olefin content of coker naphthas
increases the risk of coking on the catalyst, and
good grading becomes more important to avoid
excessive pressure drop build-up. Typically, a
hard crust layer leading to rapid pressure drop
build-up would be experienced in the top part of
the catalyst bed if the grading and reactor dimensions were not designed to handle the higher
amount of olefins. The solution to the problem
comes from a fundamental understanding of
crust formation with respect to graded catalytic
activity; heat transfer; bed void size; and rate of
olefin saturation versus temperature.
In the past, part of the solution was to grade
the top of the catalyst bed by catalytic activity
only (ie, gradually increasing catalytic activity
from the inert top layer down to the main bed by
several increments instead of having one step
from inert to maximum activity).
However this is not sufficient for high olefinic
feedstocks, since only a very small activation

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energy is required, resulting in a high temperature increase in the topmost part of the catalyst
bed even when utilising low-activity catalysts.
The key to solving this challenge, in combination
with the activity grading, is to design the reactors and the rate of treat gas to allow a sufficient
heat transfer in the axial direction, thereby
avoiding hot spots and resulting crust formation.
This problem has been overlooked in the past,
but is becoming more important as the amount
of olefins in feeds increases.
However, even with the best activity grading,
some crust and coke formation will still occur in
combination with contaminants introduced with
the feedstock. This calls for additional protection
to make sure there is a sufficient void for these
types of contaminants. Typically, this is done by
controlling the bed void size. Controlling the bed
void size is done by loading the reactor with
different sizes and shapes of grading material:
high void topping material followed by larger
rings on top of smaller rings, and underneath
these the bulk catalyst. The reason for using
rings of different sizes is to create a loading that
has a differentiated filtering effect, so the largest
contaminants introduced with the feed are
trapped in the upper layers and the smaller
particles are deposited in the lower layers.

Achieving sub-ppm sulphur and nitrogen

levels
After the removal of silica and the saturation of
olefins, the removal of sulphur and nitrogen to
very low product levels remains. The light-boiling sulphur components present in coker
naphthas are generally quite readily removed.
However, mercaptan formation through the
recombination of olefins and H2S may limit HDS
conversion. For nitrogen removal, a high-activity
HDN catalyst should be used to obtain reformergrade naphtha. The catalyst selection depends on
feedstock and product specifications. Major challenges are to select the correct pressure level and
to avoid recombination to limit the cycle length.

Hydrogen partial pressure

One of the key parameters to define is the minimum required hydrogen partial pressure. Below
a certain hydrogen partial pressure it becomes
impossible to reduce the product nitrogen to the
level required for the reformer feedstock, even
when increasing the operating temperature. The

PTQ Q1 2008 5

Recombination equilibrium constant

increase in reactor temperature

cannot make up for the loss in catalyst activity when approaching EOR.
To understand the fundamental
chemistry behind the recombination
Equilibrium
reactions, pilot plant experiments
have been carried out.
Using l-hexene as representative
of olefins in the liquid feed and a
Low WHSV
H2S/H2 treat gas mixture, three
High WHSV
mercaptans were formed: 1-, 2- and
3-hexanethiol. This observation
strongly implies that both a radical
Temperature, C
addition pathway and an elecFigure 6 Recombination of H2S and hexene as a function of temperatures. trophilic addition pathway are Q1
At low temperatures, the reaction is kinetically controlled; at high
2008 possible reaction routes. To
temperatures, it is equilibrium controlled
prove that not only terminal olefins
may undergo recombination, an
actual reactor outlet hydrogen partial pressure is experiment with cyclohexene was carried out,
a function of several parameters: total pressure; and only a single thiol (cyclohexanethiol) was
degree of feedstock vapourisation; amount of observed. It is thus necessary to take all olefin
circulated treat gas; and type of quench, liquid isomers present in the reactor into account when
product or treat gas. All these need to be consid- modelling the recombination reactions. As was
ered along with the ammonia inhibition and demonstrated, l-hexene readily isomerises into
fugacity of the reaction components to reach the the more stable 2- and 3-hexenes at typical reacoptimum catalyst activity.
tion conditions.
Hydrogen partial pressure used to be
The recombination reactions may reach equiconsidered the only factor affecting catalyst librium at high temperatures, as demonstrated
activity. However, the fugacity of the sulphur in Figure 6, where the measured equilibrium
components is dependent on the amount of treat constant (Pthiol/ Phexene PH2S) is shown and
gas being circulated. Since the treat gas-to-oil compared with the theoretical equilibrium line.
ratio has pronounced effects on the fugacities of At low temperatures, the reaction is kinetically
all reacting molecules, a more thorough analysis limited, while at high temperatures the reaction
in the design phase is needed to define the opti- is controlled by equilibrium. Such fundamental
mum treat gas amount that results in maximum studies help determine to what extent recombination reactions take place in the reactor
catalyst activity.
effluent train and to take measures to avoid
Sulphur recombination
these.
The reaction of H2S with olefins to form
mercaptans is known as recombination and is of Conclusion
particular importance in coker naphtha hydrot- Hydroprocessing of coker naphtha material
reating due to the high amounts of olefins and requires specialised catalysts and technologies to
organic sulphur in these feedstocks. The forma- overcome the challenges of the high olefin and
tion of olefins from dehydrogenation of paraffins silica content, and to produce a product meeting
is an endothermic reaction. At high reactor outlet the very stringent sulphur and nitrogen specifitemperatures, mercaptans may be encountered cations. A careful selection of process conditions
in the product, even though the recombination as well as a proper integration of the different
reaction itself is exothennic. Thus, contrary to sections within the unit make longer runs possicommon practice, it may be necessary to lower ble and ensure a better profitability. During the
the reactor temperature to reach the product last two years alone, Topse has designed more
sulphur specification. The recombination reac- than ten units processing coker naphtha
tion may then limit the cycle length, since an feedstock.

6 PTQ Q1 2008

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This article was presented at the ERTC 12th Annual Meeting

2007 in Barcelona, Spain.
Rasmus Breivik is proposal and technology manager for refining
technology at Haldor Topse A/S in Lyngby, Denmark. Breivik
earned a BSc in chemical engineering from the Technical
University of Denmark.
Rasmus Egebjerg is with Haldor Topse A/S in Lyngby,
Denmark.

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PTQ Q1 2008 7