Dealing with hydrogenation
catalyst poisons
For stable operation of a pyrolysis gasoline unit, it is crucial to know the effects
of poisons and inhibitors on catalyst performance and how to counteract them
Dirk Lose, Ernesto J Angueira and Markus Schulte CRI Catalyst
Anke Derking Shell Global Solutions International
T
he hydrogenation of so-called pyrolysis
gasoline is an important part of most liq-
uid feed steam cracker operations. Feeding
a liquid cracker with a naphtha or hydrowax
diet, the share of pyrolysis gasoline can be as
high as 20% of the cracker product mix.1
The purpose of hydrogenation of pyroly-
sis gasoline is to eliminate highly reactive spe-
cies deemed to polymerise and potentially cause
fouling and plugging, such as alkynes, diole-
fins, styrene and olefin compounds, as well as
to remove sulphur, while minimising losses
of aromatics.
This is commonly achieved by hydrogenation in
two subsequent stages. The first stage is a trickle
phase operation employing palladium or sul-
phided nickel catalyst to remove alkynes as well
as diolefinic and styrenic species. The second
stage is a vapour phase operation employing sul-
phided nickel molybdenum (NiMo) and cobalt
molybdenum (CoMo) catalysts to remove mainly
olefins and convert sulphur compounds to hydro-
gen sulphide.
Targeting reliable and stable operation, the
performance of the catalyst is essential. Knowing
the feed composition, operating parameters, and
start of run catalyst activity, one can model and
predict the catalyst’s performance, inclusive of
cycle length, for given end of run criteria. This
includes adjustments of the model for known
feed poisons and inhibitors. If catalyst activity
is permanently reduced by a feed contaminant,
one classifies such a contaminant as a poison. If
catalyst activity is restored after contact with the
specific feed contaminant has been stopped, one
classifies such a contaminant as a temporary poi-
son or inhibitor.
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However, a great advantage is the flexibil-
ity to use a broad range of cracker feedstocks.
Inherent with the benefit of such flexibility, the
composition of the feed and the catalyst poisons
and inhibitors in the feed change by nature and
quantity.
For stable operation of a pyrolysis gasoline
unit, it is of high value to know the effects that
various poisons and inhibitors have on the per-
formance of the catalyst as well as to know if and
what measures can be taken to counteract and to
restore the catalyst’s performance.
Feed contaminants
While there are numerous literature sources
available on catalyst poisons and inhibitors,2,3,4
we focus in this study on a few, which are sulphur
(as CS2), nitrogen (as ethylamine and pyridine),
silicon (as hexamethyldisiloxane) and lead (as
tetraethyl lead).
Most feed sulphur contaminants originate from
cracker feeds where they are commonly found
in the range 50-250 ppm. However, some sul-
phur also originates in intentionally added com-
ponents such as dimethyl disulphide, which is
deemed to convert to hydrogen sulphide (H2S) in
the radiant coils and to passivate the nickel sites
on the tube surface and reduce coking rates (see
Figure 1).1
While mercaptans and organic disulphides
are mainly cracked to H2S in the radiant coils
and later washed out in the caustic column,
thiophenic, benzothiophenic, and other com-
plex sulphur compounds are reasonably stable
and end up in the pyrolysis gasoline fraction.
The same happens to carbon disulphide (CS2),
which mostly originates from the cracker
PTQ Q1 2018 1
 Sulphur Silicon
e.g. DMDS e.g. HMDS
Feed Furnace Hot Compression
Sulphur section
Drying
Nitrogen Quench
Metals
Others
Figure 1 Simplified cracker scheme indicating origin of contaminants. DMDS = Dimethyldisulphide;
HMDS = Hexamethyldisiloxane; DMF = Dimethylformamid
feed passing the radiant section without
conversion.
The possibility of CS2 formation in the radi-
ant section has to be considered as well. Up to
the 1950s, CS2 was indeed produced from the
elements at about 800°C.4 However, the partial
pressures of sulphur and carbon in the radiant
section are mostly regarded as too low and thus
formation of CS2 can only contribute margin-
ally to the overall balance. It has been observed
that in many imported feeds the level of CS2 has
recently increased remarkably, causing trouble in
the downstream pyrolysis gasoline hydrogenation
reactors.5
Nitrogen containing contaminants also originate
from the cracker feed and from extraction solvents
such as N-formylmorpholine, dimethylformamide
or N-methyl-2-pyrrolidone. Amines are cracked
mostly to ammonia and hydrogen cyanide, while
cyclic structures such as pyridine and pyrrole
are stable and make their way into the pyrolysis
gasoline.6
Silicon is of some interest as additives contain-
ing silicon are frequently added in the quench
tower to reduce foaming and support water
organic separation. As a matter of practice, some
of the silicon additives arrive with the pyrolysis
gasoline feed. Potentially, silicon can accumulate
on the catalyst surface and form glass structures,
for instance under conditions in which the cata-
lyst is regenerated, which deactivates the catalyst
significantly or totally.7
Lead is a metal less frequently found than
nickel, vanadium or mercury, but it is commonly
found in liquid feedstocks and mostly as an
organolead component.8
2 PTQ Q1 2018
Ethylene Propylene Nitrogen C4s, C5s
e.g. DMF
Cold train C3 C4, C5 extraction/ First stage
and ethylene C4 fractionation gasoline
recovery hydrogenation
C5
Gasoline
Experimental set-up
A bench scale testing unit was employed to deter-
mine the impact of various contaminants on cat-
alyst activity. The unit was fully automated and
utilised a process control system. Liquid sam-
ples were taken with an automatic sampler. The
testing unit consisted of two independent reactor
systems, allowing for two tests to be performed
in parallel. Two separate feed tanks allowed for
easy switching between straight pygas and pygas
spiked with the desired catalyst poison.
The adjusted testing conditions mimic the typ-
ical conditions of a first stage pygas unit, but
no recycle flow of hydrogenated product was
applied. The weighted average bed temperature,
adjusted to achieve a defined start of run activ-
ity of fresh catalyst, was kept unchanged after
the switch to ‘poisoned’ feed. At the end of each
run, initial conditions were adjusted to monitor
the loss of activity (point of return). Hot hydro-
gen strip was performed to evaluate the possibil-
ity of regeneration of the catalyst after exposure
to contaminants.
The catalyst used for these experiments was
a CRI first stage nickel catalyst. The shape
of the catalyst was a 2.5mm trilobe extru-
date. The catalyst was loaded in the pre-
sulphided form and in situ reduction was per-
formed at 750°F (400°C) to make it ready for
use. To ensure proper radial distribution and to
minimise wall effects, the catalyst was diluted
with an inert material. A fresh catalyst sample
was used for every test. The results of the poison-
ing experiments are benchmarked with a refer-
ence test of fresh catalyst without poisons.
The main criterion to evaluate the catalyst’s
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performance was the change of
hydrogenation activity of sty- av run data without poison + confidence belt
rene. Liquid samples were ana- Pygas with poison
lysed to determine the content of After HHS
slipped contaminant. The spent
catalyst samples were tested for
accumulation of poisons.
The health and safety risks

Activity
of the planned poisons were
assessed prior to the begin-
ning of the experiments. A risk
assessment was conducted for
every poison.

Impact of sulphur as carbon

Start-up Poison present No poison
disulphide No poison No adaption of parameters Point of return (POR)
The first tests were performed After hot hydrogen strip
with sulphur as CS2 and the Time
main results are depicted in
Figure 2. After a start-up period Figure 2 Impact of CS2 (20 ppmw S) on styrene conversion
to confirm stable and relia-
ble conditions, the feed was
switched to contain 20 ppmw
sulphur as CS2, corresponding to
24 ppmw CS2. The impact of the
catalyst’s performance was pro-
nounced. Conversion dropped
Activity

by up to 75% of the initial activ-

ity. After equilibrium was
reached, the performance of
the catalyst became more sta-
ble but steady deactivation could av run data without poison + confidence belt
still be observed. A temperature Pygas with hexylamine
increase (not shown in the fig- Pygas with pyridine
ure) was required to match the Start-up Poison present No poison
activity in the reference exper- No poison No adaption of parameters Point of return (POR)
iment. The effect of CS2 was Time
found to be reversible. Switching
to the standard feed resulted Figure 3 Impact of hexylamine and pyridine (50 ppmw N) on styrene
in almost complete recovery of conversion. The key message here is that if a feed contains a high load of
activity over time. After a hot basic nitrogen, it is possible to counteract the deactivation with an increase
hydrogen strip procedure was in inlet temperature
performed, activity was com-
pletely restored. uct. Post mortem analysis of the spent catalyst
It was demonstrated that the adsorption equi- revealed that no additional sulphur accumulated
librium of sulphur on the catalyst was established on the catalyst and the residual sulphur found
in the first hours of the run. During this period, was in agreement with the total amount of sul-
the sulphur partially adsorbed onto the catalyst phur slipping with the liquid product.
and partially passed the catalyst bed, slipping The key message here is that if a CS2 spike
with the product. After adsorption equilibrium can be expected, drop of activity can be antic-
was established, the complete amount of sulphur ipated by a preventative increase in operating
fed to the reactor was detected in the liquid prod- temperature.

www.digitalrefining.com/article/1001463 PTQ Q1 2018 3

 formance of the catalyst stabi-
lised. Monitoring of nitrogen
content in the reactor product
showed that the adsorption equi-
librium was fully established
very slowly after a long time
Activity

on stream. During this period,

nitrogen was adsorbed onto the
1 wtppm 5 wtppm 10 wtppm 25 wtppm 35 wtppm
fresh catalyst, resulting in low
concentrations of nitrogen in the
liquid samples. Once adsorption
av run data without poison + confidence belt was completed, all dosed nitro-
Pygas + Si (1– 35 wtppm)
gen passed through the reactor
Start-up Poison present No poison and could be found in the liq-
No poison No adaption of parameters After hot uid product. When dosing of the
hydrogen strip
Time amine was stopped, hysteresis
was observed. It took about 30%
Figure 4 Impact of silicon as siloxane (1-35 ppmw Si) on styrene conversion. longer to desorb the nitrogen.
The key message here is that the effect of silicon as siloxane is low at first The initial performance recov-
stage pygas conditions ered after hot hydrogen strip as
well as after resetting the refer-
ence conditions.

Impact of organic silicon as

siloxane
Hexamethyldisiloxane was tested
because it is a good representa-
Activity

tive of the group of anti-foaming

agents that are a typical source
of silicon contamination in pygas
0.1 wtppm 0.5 wtppm 1.0 wtppm
feeds. Initial results show silicon
av run data without poison + confidence belt to have a weaker poisoning effect
Pygas + Pb (0.1– 1.0 wtppm) on the presulphided nickel cat-
Start-up Poison present No poison alyst than was expected. Due to
No poison No adaption of parameters After hot the weak effect, a higher amount
hydrogen strip of silicon was adopted to obtain
Time
a visible effect. The concentra-
Figure 5 Impact of lead (as tetraethyl lead, 0.1-1 ppmw Pb) on styrene tion could be increased up to 35
conversion. The key message here is that the tests revealed a progressive ppmw without a negative effect
poisoning of the catalyst. Activity can be restored but poison remains on the on catalyst activity. Most of the
catalyst silicon slipped through the first
stage pygas reactor. Figure 4
Impact of (basic) nitrogen as primary amine shows the impact of silicon on styrene conversion
Basic amines are considered to be the most reac- after start-up with undoped feed when the silicon
tive components in the group of nitrogen con- concentration was increased in steps from 1 ppmw
taining compounds. Hexylamine as primary to 35 ppmw. Eventually, the ability to perform a
amine and pyridine as heterocyclic aromatic hot hydrogen strip after treatment with silicon was
amine were tested and the effect differed from checked with no unexpected results regarding cat-
CS2 (see Figure 3). The response of hexylamine alyst activity.
was less strong and required more time to sta-
bilise than upon spiking with pyridine. Once Impact of organic lead
adsorption equilibrium was established, the per- Lead is generally found in liquid feedstocks and

4 PTQ Q1 2018 www.digitalrefining.com/article/1001463

natural gas liquids. It is rarely found as elemen-
tary lead, but most likely as an organolead com-
ponent such as tetraethyl lead (TEL) which ends
up in the pygas fraction. TEL is considered to be a
representative component for other organometal-
lic contaminants. The experiment with TEL may
therefore shed some light on the impact of other
metals such as mercury which could not be tested
due to potential health hazards and manageability
in the laboratory.
After obtaining the first results, the amount of
lead was adopted to demonstrate its effect more
clearly and the results are shown in Figure 5.
After start-up with fresh feed, the lead concen-
tration was increased in steps from 0.1 ppmw
to 1 ppmw. The loss of activity built up linearly
with the amount of accumulated lead. When the
lead amount was increased, conversion dropped
below the reference data and continued to fall.
The drop of activity was less severe when the
amount of lead was constant at 0.1 ppmw. The
liquid reactor product contained about 20% of
the dosed lead. It was possible to perform a hot
hydrogen strip to restore activity, even when
some accumulated lead remained fixed on the
active sites and could not be removed by regen-
eration. Spent catalyst analysis confirmed that
most lead remained on the catalyst and, after the
switch back to undoped pygas, lead in the reac-
tor outlet product totally disappeared, which
means that the accumulated lead was fixed on the
catalyst. This was an intriguing outcome show-
ing how the lead is linked to the catalyst before
or after the hot hydrogen strip. A possible theory
is migration of lead to the nickel core during the
hot hydrogen strip, but further investigation is
needed.
Conclusion
The impact of several poisons on a typical sul-
phided nickel catalyst used in the first stage
pygas hydrogenation system was evaluated.
Selection of poisons for the study was driven by
relevance or known incidents in the industry,
availability of a representative component, and
related risk assessments.
This experimental programme aimed to estab-
lish the maximum load values for individual con-
taminants by dosing representative compounds
in the pygas feed and monitoring catalyst per-
formance as a function of contaminant concen-
trations in the feed over time. Representative
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compounds of sulphur, nitrogen (basic), lead, sil-
icon and others were tested. The main areas stud-
ied in the testing included the effect on catalyst
activity, the effectiveness of hot hydrogen strip-
ping to restore activity, and the accumulation
of the contaminants and carbon on the catalyst
surface.
In all cases, most if not all of the catalyst’s
original activity was recovered by performing
hot hydrogen stripping. The impact of the tem-
porary poisons CS2 and basic nitrogen can be
mitigated by a proactive increase in tempera-
ture. Silicon as siloxane did not deactivate the
catalyst and lead showed a linear accumulation
on the catalyst, leading to a shortening of cycle
length over time.
References
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European Magazine, 4/2009, 191-196, Urban-Verlag Hamburg/
Wien GmbH.
2 Bartholomew C H, Agrawal P K, Katzer J R, Sulphur poisoning
of metals, Advances in Catalysis, Vol 31,135 ff., Academic Press
Inc.,1982.
3 Bartholomew C H, Mechanism of catalyst deactivation, Applied
Catalysts, General 212, 17-60, Elsevier, Amsterdam, 2001.
4 Butt J B, Petersen E E, Activation, Deactivation and Poisoning
of Catalysts, Academic Press Inc., San Diego, 1988.
5 Madon H N, Stickland-Constable R F, Ind. Eng. Chem., 50 (8),
1189-1892, 1958.
6 Proceedings of EEPC 2016, Prague and 2017, Valencia.
7 Weissermehl K, Arpe H-J in Industrial Organic Chemistry, 3rd
edition, 107-124, VCH Publishers, Inc. New York, 1997.
8 Didillon B et al in Studies in Surface Science and Catalysts,
Bartholomew C H, Fuentes G A (Eds), Vol 111, 447-454, Elsevier,
1997.
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Dirk Lose is a Technical Service Engineer with CRI Catalysts in
Leuna, Germany. He provides technical support in catalytic
hydrogenation in processes downstream of steam crackers in
Europe and the Middle East. He holds a diploma in chemistry and
a PhD in physical chemistry from the Martin Luther University,
Halle, Germany.
Ernesto J Angueira provides technical support in catalytic
hydrogenation in processes downstream of steam crackers
with CRI-Criterion Catalyst. He holds a BS degree in chemical
engineering from the University of Puerto Rico, and MS and
PhD degrees in chemical engineering from Georgia Institute of
Technology.
Markus Schulte is a Senior Account Executive with CRI Catalyst.
With a technical and commercial background in catalytic
applications and markets, he holds a diploma and a PhD in
chemistry from the Technical University of Munich.
PTQ Q1 2018 5
 Anke Derking is a Senior Technologist with Shell Global Solutions
B.V. With 32 years of experience in heterogeneous catalysis,
chemical engineering and process safety, she holds a MSc degree
in chemistry from the University of Amsterdam and a MSc degree
in chemical engineering from TU Twente, the Netherlands.
6 PTQ Q1 2018
LINKS
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