Catalyst passivation for safer, more
efficient turnarounds
Eliminating inert entry for catalyst changeout in a hydrocracker
Alvaro Barrueto ENAP Refinerías
Ian Baxter and Gary Welch Cat Tech International
S
ince hydrotreating and hydrocracking were
introduced to the refining industry in the
mid-20th century, it has always been a
struggle to safely remove the catalyst from the
reactors. These catalysts typically contain a com-
bination of molybdenum or tungsten with nickel
or cobalt. The catalysts are manufactured as sta-
ble metal oxides. During the activation process,
the metal oxides are converted to sulphides.
These metal sulphides are very reactive and,
when exposed to air, can spontaneously ignite.
This not only creates a fire hazard but can also
release toxic sulphur dioxide, making it difficult
to remove them safely from reactors.
In the early days, refiners addressed this prob-
lem by performing an in situ regeneration or pas-
sivation of the catalyst by heating with steam/
air or nitrogen/air under controlled conditions.
There are two major problems with this solu-
tion. First, it is very time consuming and would
keep the unit off stream for days. Secondly, it fre-
quently resulted in the release of toxic sulphur
oxides to the atmosphere. In situ practices were
essentially outlawed by the clean air regulations
of the 1970s and 1980s.
The industry solution to these regulations was
to remove the catalyst under nitrogen. With air
eliminated, the catalyst could be safely unloaded,
packaged in hermetically sealed containers, and
sent for disposal, reclamation or regeneration.
This created a new industry for ‘catalyst handlers’.
These professionals would enter reactors under
nitrogen with breathing apparatus to vacuum or
shovel out catalyst. Unfortunately, this is a very
dangerous operation and has resulted in accidents
and fatalities over the years. The dangers are even
more severe with newer multi-bed reactors which
are difficult to egress in an emergency. The equip-
ment and procedures have improved to the point
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that incidents are rare, but there are still fatalities
in the industry today.
History of catalyst passivation
Catalyst Passivation Technology has been used
successfully to treat over 350 million kg of cat-
alyst to date, with 151 reactors treated in 2017
alone. Its development history started in the
mid-1980s in Japan where Kashima Engineering
Company (KEC) and Softard Industries devel-
oped the technology for passivating self-heating
catalysts so that they could be safely removed
under air. This has the obvious advantages
of eliminating the need for inert entry opera-
tions. The technology was applied primarily to
resid desulphurisation units because of the chal-
lenges they afforded with multi-bed reactors and
agglomerated catalyst. The treatment process
involves the application of a proprietary mixture
of organic compounds to a reactor system while
under oil recirculation during the cooling and
shutdown process. These compounds have the
ability to coat all surfaces with which they come
into contact. This includes reactor internals but
most importantly the catalyst itself. This organic
film retards oxygen penetration to the reactive
metal sulphide surfaces and retards the danger-
ous and exothermic oxidative reactions. This is
somewhat different to the conventional shut-
down procedure which involves a hot hydrogen
strip. The process oil is usually flushed from the
unit and replaced with a lighter oil of prescribed
viscosity and other parameters and is termed the
‘carrier oil’. Once the unit is flushed and the pro-
cess oil replaced, it is put on oil recirculation fol-
lowed by injection of the organic compound.
KEC and Softard optimised this technology
through application to their native refinery and
have now expanded throughout the Far East. Cat
April 2018 1
 ated with nitrogen and confined
space entry. Cat Tech started
talking to ENAP in 2015 about
its catalyst passivation tech-
nology as a way to shorten the
shutdown duration and make
reactor unloading safer. In
March 2016, ENAP elected to
use passivation technology in a
trial application on its smaller
diesel hydrodesulphurisation
(HDS) unit and, following its
success, then applied it to their
Figure 1 Mild hydrocracker at Bio Bio refinery, Chile MHC in the same year.

Benefits of catalyst passivation

300 Cobalt/moly catalyst Although the opportunity to
250 Untreated eliminate inert entry was cen-
Treated tral to developing the technology,
200
there are many other advantages
∆T, ºC

150 in catalyst passivation. These can

100 Sulphur Carbon Autoignition be categorised in the following
burn burn
sections.
50

0 Safety: opportunity to
−50
70 120 170 220 270
Temperature, ºC
Figure 2 Thermogram of treated and untreated catalyst
Tech International Ltd, a specialist catalyst han-
dling company, licensed the technology for appli-
cation in Europe, Asia, Africa, Australia and the
Americas.
ENAP interest
ENAP Refinerías S.A. operates two refineries in
Chile, Bio Bio and Aconcagua, with a combined
distillation capacity of 220 000 b/d. The refiner-
ies supply 80% of domestic fuel requirements and
also export part of their production to Peru. At
the Bio Bio refinery is a 20 000 b/d mild hydro-
cracker (MHC) unit containing about 247 000
kg of fresh basis catalyst. It consists of four reac-
tors in series flow, processing vacuum gasoil (see
Figure 1).
Historically, the unit has experienced unload-
ing difficulties due to agglomerated catalyst
requiring hazardous inert confined space work
to perform vacuum extraction. ENAP was look-
ing for other options to reduce the risks associ-
eliminate inert entry
320 370 420 The self-heating or pyrophoric
nature of the catalyst and dust
is suppressed or eliminated by
the passivation treatment. This
allows the safe handling of cata-
lyst in an air atmosphere.
Figure 2 illustrates the passivating effect of
the treated catalyst. The thermogram in Figure
2 shows the heat released by catalysts as they
are heated. The red line represents an untreated
catalyst whereas the blue line is the same cata-
lyst treated by the passivation process. As can
be seen, when the untreated sample reaches
about 120°C, an exotherm is observed. This is
the reaction of the metal sulphides with air. As
the temperature is further increased, a second
exotherm occurs around 250°C. This is carbon
and coke on the catalyst burning. The treated
sample does not demonstrate a significant exo-
therm until 300°C. This demonstrates the dra-
matic stabilisation provided by the treatment.
If catalyst is removed under air, it is noted that
many reactors are made of austenitic stainless
which may become sensitised and prone to the
phenomena of polythionic acid stress corro-
sion cracking (PSCC). Formation of polythionic

2 April 2018 www.digitalrefining.com/article/1001490

acid requires three things to be present: sul-
phide corrosion products, oxygen and moisture.
In the case of unloading in air, NACE interna-
tional standards1 provide guidelines for protec-
tion of the surfaces of austenitic stainless steel
through the exclusion of water using dehumidi-
fied air.
Dust-free operation
Dust from catalyst handling operations typi-
cally contains iron and catalyst metal sulphides
which are both toxic and pyrophoric in nature.
These types of dust are a risk to people and the
environment and present a challenge to everyone
involved in catalyst handling. In particular, com-
pounds of nickel are under increasing European
regulatory scrutiny. With passivated catalyst,
dust and fines adhere to the treated catalyst sur-
faces, resulting in a dust-free handling operation.
The technology can therefore be applied as an
effective risk control measure, contributing to a
safer system of work.
Time savings: reactor shutdown time reduced
The modified shutdown procedure eliminates
the need for performing a hot hydrogen strip
of the spent catalyst. Adding this with the abil-
ity to cool the reactor bed under liquid oil circu-
lation with its superior heat transfer capabilities
can typically reduce conventional shutdown time
by some 12-36 hours. This can have a positive
impact on the time value of the unit, particularly
if it is on the critical path of a turnaround.
Mitigation of high LELs
Many units using a conventional shutdown
method have difficulty in achieving acceptable
flammable vapour concentrations (LEL). The
traditional hot strip method has the potential to
produce volatile hydrocarbons through crack-
ing reactions of residual oil left on the catalyst.
Naphtha range material can be produced as a
consequence and result in LELs in excess of those
deemed safe for reactor entry. This can result in
significant standby delays whilst the reactor is
purged with nitrogen in an attempt to remove
LEL. As a consequence, controlling vapour con-
centrations to well below acceptable LEL limits
is a major consideration for refiners. The passi-
vation treatment is effective at mitigating LELs
through careful selection of suitable carrier oil
and the modified shutdown procedure.
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Passivation application procedure: MHC, ENAP
The passivation process employs the injection of
a proprietary organic chemical to a reactor sys-
tem while under oil recirculation during the cool-
ing and modified shutdown process. The details
of the shutdown must be tailored for each appli-
cation depending on such considerations as unit
configuration, catalyst type, and local practices.
The following modified shutdown procedure was
agreed between Cat Tech and ENAP for their
MHC.
Unit feed rate and unit temperature were
simultaneously reduced. The reduction in feed
rate is necessary to avoid excessive unit pres-
sure drop whilst the unit is cooling down under
oil circulation. At the same time, the flow must
be high enough to maintain good liquid distri-
bution in the reactor for treatment of the cata-
lyst. The reactor temperature is reduced to avoid
unwanted cracking and desulphurisation reac-
tions during the chemical application. During
this initial cooling stage, the normal process feed
was displaced from the unit and replaced with
the identified carrier oil. The carrier oil selected
was a middle distillate with a flash point of >85°C
and a viscosity of ~4 cSt. Samples were periodi-
cally taken at the stripper bottom and the feed
tank and analysed for viscosity and flash point
to monitor the progress of the flushing opera-
tion. Once confirmed as flushed, the unit was put
on internal oil recycle from the fractionator bot-
toms back to the feed surge drum. When target
conditions were met with regard to temperature
and flow rate, in this case 235°C and 120m3/h,
the passivating chemical was injected over a two
hour period at the suction side of the feed pump
and this was followed by 10 hours of circulation
whilst continuing to cool the reactors. ENAP
wanted to take advantage of cooling under oil
circulation as far as possible due to its superior
heat transfer capabilities. A target temperature
of 130°C was achieved which was 20°C above the
minimum depressurisation temperature of the
unit. Target temperature is dependent on many
variables including oil viscosity, unit pressure
drop, minimum depressurisation temperature,
compressor characteristics and other variables.
Once the target temperature was achieved, the
unit was de-oiled using maximum hydrogen
gas flow. The unit was then depressurised and
degassed according to normal procedures whilst
cooling to entry temperatures. Reactor heads
April 2018 3
 safety and reliability of catalyst
1 Cool and flush 4 De-oiling changeout for the MHC. Alvaro
450 2 Injection 5 Depressure and
final cooling
Barrueto, Maintenance Engineer
3 Chemical recycle &
400 catalyst treatment Hot strip at the Bio Bio refinery, said, “The
350 Catalyst passivation technology ena-
Temperature, ºC

1 passivation
300 bled us to apply a safer system
250 of work, eliminating two of the
200 2 major hazards associated with
150 3
catalyst removal, nitrogen while
100
4
5
unloading catalyst and inert
50 Time saving = 40 hours
entry into confined spaces. The
0
modified shutdown procedure
1 7 13 19 25 31 37 43 49 55 61 67 72 allowed us to reduce the overall
Time, hours downtime and gave us access to
the reactors sooner.”
Figure 3 MHC comparative shutdown timeline The foregoing is not intended
to be an endorsement of the pas-
were removed and the vapour space analysed for sivation technology by ENAP Refinerías S.A. Each
hydrocarbon vapour (LEL), CO, H2S and SO2. reactor unit must undergo a comprehensive engi-
neering evaluation to assess its suitability and the
Results refiner must exercise their own independent judg-
In April 2016, the MHC unit was successfully ment to decide whether the technology is appro-
shut down with the catalyst passivation technol- priate for use.
ogy. Figure 3 compares and outlines the steps
References
involved in the modified and prior shutdown
1 NACE – SP0170-2012, Protection of Austenitic Stainless
procedures. As can be seen, elimination of the Steels and Other Austenitic Alloys from Polythionic Acid Stress
hot hydrogen strip and the ability to cool under Corrosion cracking during Shutdown of Refinery Equipment.
liquid oil circulation allowed the unit to be shut
down some 40 hours earlier than the traditional Alvaro Barrueto works as a Maintenance Engineer for ENAP Bio
shutdown method. On opening the reactor man- Bio Refinery in Chile. He is in charge of the refinery’s catalyst
ways, gas samples were taken in all four reac- replacement operations, as well as supporting maintenance
activities in different units.
tors and found to be LEL free. The reactors were
Ian Baxter is the Technical Manager with Cat Tech International
quickly and sequentially turned over to air, ena-
Ltd and has over 25 years’ experience in the refining and
bling catalyst unload operations to be expedited chemical Industry. Based in the UK, he provides technical
in an atmosphere that was not immediately dan- expertise across a number of technologies including Catalyst
gerous to life or health (IDLH). The catalyst was Passivation Technology.
well passivated, showing no signs of reactivity, Gary Welch has over 40 years’ experience in the petroleum
and all toxic dust and pyrophoric material elimi- refining industry, specialising in hydrotreating catalysts and
nated. The majority of catalyst (~90%) had to be operations. His early career was spent with Shell Oil Company
removed by vacuum extraction as a consequence in research and in positions of sales and manufacturing of
of its agglomerated nature and reluctance to hydrotreating catalysts. He now operates as an independent
dump. Historically, this would have involved per- consultant and consults for Cat Tech International on the Catalyst
Passivation Technology.
sonnel entering a nitrogen filled confined space
to perform these works. In this instance, some
239 hours of confined space works associated
with mechanical tray work and catalyst removal
LINKS
was all performed in an air atmosphere.
More articles from: Cat Tech International
Conclusion More articles from the following categories:
Catalyst Passivation Technology provided an Catalysts and Additives
alternative methodology for ENAP to improve the

4 April 2018 www.digitalrefining.com/article/1001490