Eliminating inert entry for catalyst
changeout
Cat Tech International Limited
S
ince hydrocracking and hydrotreating cata-
lyst were introduced to the refining industry
in the mid-20th century, it has always been
a struggle to safely remove catalyst from the reac-
tors. The catalysts are typically manufactured as
stable metal oxides; however, during their activa-
tion the metal oxides are converted to sulphides.
These metal sulphides are very reactive and, when
exposed to air, can spontaneously ignite. The
industry addressed the problems by removing the
catalyst under nitrogen: an inert atmosphere. With
air eliminated, the catalyst can safely be removed,
but confined space entry into a nitrogen filled
atmosphere is inherently a dangerous operation.
The dangers are amplified with multi-bed reac-
tors that are difficult to egress in an emergency.
Even today, fatalities occur in the industry despite
improvements in both equipment and systems/
procedures.
In response, Kashima Engineering (KEC) and
Softard Industries in Japan developed a technol-
ogy for passivating self-heating catalysts so they
could safely be removed under air. This has the
obvious advantage of eliminating what is com-
monly referred to as the most dangerous oper-
ation in refineries today: inert entry operations.
It employs the application of a proprietary mix-
ture of organic compounds to the catalyst during a
modified reactor shutdown procedure. These com-
pounds have the ability to coat all the catalyst sur-
faces and pores with an organic film that retards
oxygen penetration to the reactive metal sulphide
surfaces. This severely retards the dangerous and
exothermic oxidative reactions. Figure 1 illustrates
the passivating effect of the treated catalyst, show-
ing the heat released from a CoMo sulphided cata-
lyst as it is heated in air. The red line represents an
untreated catalyst whereas the blue line is the same
catalyst treated by the passivation technology. As
can be seen when the untreated sample reaches
about 120°C an exotherm is observed. This is the
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reaction of the metal sulphides reacting with air. As
this temperature is further increased, a second exo-
therm occurs around 270°C. This is the carbon and
coke on the catalyst burning. The treated catalyst
does not demonstrate a significant exotherm until
300°C. This shows the stabilisation provided by the
passivation technology.
A case study describes how ENAP Refinerías
performed catalyst removal under an air atmos-
phere for a mild hydrocracking unit (MHC). The
20 000 b/d unit processes vacuum gasoil and con-
sists of four fixed bed reactors in series contain-
ing around 247 000 kg of fresh basis catalyst. On
25 March 2016, MHC feed rate and unit temper-
atures were simultaneously reduced. The reduc-
tion in feed rate is necessary to avoid excess unit
pressure drop whilst the unit is cooling down. At
the same time the flow must be high enough to
maintain good liquid distribution in the reac-
tor for treatment of the catalyst. During this cool-
ing stage, the normal process feed is displaced
from the unit and replaced with a carrier oil of
prescribed viscosity and other properties, in this
case a middle distillate. Once the unit was fully
flushed it was put on oil recirculation from frac-
tionator bottoms back to feed surge drum. When
reactor temperatures were around 250°C the pas-
sivation additive was injected over a two-hour
300
Untreated catalyst
250
Treated catalyst
200 Auto-ignition
Sulphur burn
150
∆T, ºC
Carbon burn
100
50
0
−50
70 120 170 220 270 320 370 420
Cobalt/moly catalyst temperature, ºC
Figure 1 Thermogram of treated and untreated catalyst
PTQ Q1 2018 1
 period at the suction side of the feed drum pump
and this was followed by eight hours under oil cir-
culation to treat the catalyst bed whilst continuing
to cool the reactors. Once the target temperature
was achieved, in this case 130°C, the unit was
de-oiled, depressurised and degassed according
to normal procedures, followed by final cooling to
entry temperature. This modified shutdown proce-
dure is somewhat different to the conventional hot
hydrogen strip shutdown method but can typically
save 12-36 hours on reactor shutdown time alone.
Reactor heads were removed and analysed for
hydrocarbon vapour (LEL), CO, H2S and SO2. In
all four reactors gas samples were taken and found
to be LEL free. The reactors were quickly and
sequentially turned over to air, enabling catalyst
unload operations to be expedited in a non-imme-
diately dangerous to life or health (IDLH) atmos-
phere. The catalyst was well passivated, showing
no signs of reactivity and all dust and pyroph-
oric material eliminated. Catalyst removal was all
completed in an air atmosphere, ~21% oxygen. In
summary, the opportunity to eliminate the haz-
ards associated with inert entry met with the refin-
er’s expectations. Alvaro Barrueto, maintenance
engineer for Bio Bio refinery, ENAP said, “Catalyst
2 PTQ Q1 2018
passivation technology enabled us to apply a safer
system of work, eliminating two of the major haz-
ards associated with catalyst removal, nitrogen
while unloading catalyst, and inert entry in con-
fined spaces. The modified shutdown procedure
allowed us to reduce the overall downtime and
gave us access to the reactors sooner.”
Cat Tech licenses the technology for application
in Europe, Asia, Australia, Africa and Americas
and has many examples of commercial applica-
tions globally. In the last two years alone, over 200
reactors have been treated with the passivation
technology.
Cat Tech International Limited
For more information: sales@cat-tech.com
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