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Catalyst Passivation for Safer

Reactor Entry
2008 AIChE Midwest Regional Conference
September 22, 2008
J . Gary Welch, Ph.D. Tanecia Heard
Cat Tech, LLC BP
Houston, TX Whiting, IN
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Refinery Hydrotreating Reactors
Refinery hydrotreating
reactors typically contain
catalysts composed of the
following elements:
Molybdenum (Mo), Nickel
(Ni), Cobalt (Co).
Catalysts can either be
supplied in an oxide state or
a pre-sulfidedstate.
Catalyst are removed from
reactors in a highly reactive
sulfidedstate.
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Catalyst Properties
Catalysts are used to increase the rate of reaction
in reactive processes.
Active catalysts have both pyrophoric and self-
heating characteristics which require them to be
handled under a nitrogen atmosphere.
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Nitrogen Usage in a Refinery
Nitrogen has numerous safety applications within
a refinery:
Inerting equipment to prevent
flammable atmospheres
Welding Operations
Purging equipment for maintenance
Removing air from equipment prior
to start-ups
Although nitrogen is not toxic, it can
be very harmful when localized in
higher concentration than normally
found in air.
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Hazards of Nitrogen
Nitrogen is an aphyxiant in its
gas/ vapor phase.
Aphyxiants can cause death or
unconsciousness by suffocation.
Aphyxiants are especially
dangerous in confined or
enclosed spaces.
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Areas Where Incidents Occurred
A case study conducted by the CSB revealed that 85
incidents of N
2
asphyxiation during the period of 1992-2002
resulted in 80 deaths and 50 injuries.
14%
13%
5%
6%
62%
Manufacturing/industry
Trenches, manhole covers (not
identified)
Maintenance activities (not
necessarily at manufacturing sites)
Laboratories
Miscellaneous (including medical
facilities and transportation)
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Catalyst Handling
In the 1970s, catalyst
handling companies
developed technology
for entering reactors
under nitrogen with life
support equipment to
remove catalyst.
Catalyst removal is
typically done by
vacuuming or dumping
through nozzles at the
bottom of the reactor.
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Catalyst Passivation
Cat Tech licenses a novel technology for
passivating hydroprocessing catalysts
allowing removal under breathable air.
This technology is known as CATnap
TM
BP decided to evaluate the CATnap
TM
technology to minimize hazardous
operations associated with inert reactor
entry.
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BP Test Case - Blending Oil Unit (BOU)
BOU is a gas oil
hydrotreater located at the
BP Whiting Refinery
Design Specifications:
19,000 B/ D capacity
254,000 lbs of Ni/ Mo catalysts
One Reactor (3 beds of
catalysts)
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Why the BOU?
Ideal for test case with single reactor and simple oil/ gas
flow.
The unit operated on gas oil which was suitable as a
carrier oil for chemical injection.
Size is large enough to offer a real test of the technology.
Requires people inside the reactor vacuuming catalyst for
four days or more during catalyst changeouts.
Previous shutdown procedure already had oil wash and
cold hydrogen sweep which is ideal for CATnap
application.
Offered sufficient lead time to work out issues, write job
notes, perform all safety reviews and handle internal
Management of Change procedures.
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What is CATnap
TM
?
A proprietary process for treating catalyst during shutdown
to render it safe to handle and unload in air
Passivating chemical is injected into a recycle oil steam
while the unit is cooling down
The chemical coats the catalyst surface
Catalyst can be safely handled and
unloaded from the reactor under air
avoiding hazardous inert entry
procedures
The coating retards oxygen
penetration to the catalyst surface
thereby inhibiting any pyrophoric or
self-heating characteristics
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Thermogram of Treated and Untreated
Catal yst
-50
0
50
100
150
200
250
300
70 120 170 220 270 320 370 420
Temperature, C
D
e
l
t
a

T
,

C
Carbon Burn
Sulfur Burn
Autoiginition
CATnap Treated
Untreated
Cobalt/Moly Catalyst
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History of CATnap
1984 CATnap
TM
introduced in J apan
Met with rapid success, especially with resid units
1991 Cat Tech licensed CATnap
TM
technology
1998 Changes in spent catalyst classification
Led to de-emphasis of CATnap
TM
2005 Re-introduction of CATnap
TM
Driven by new emphasis on safety and unit economics
History of CATnap
1984 CATnap
TM
introduced in J apan
Met with rapid success, especially with resid units
1991 Cat Tech licensed CATnap
TM
technology
1998 Changes in spent catalyst classification
Led to de-emphasis of CATnap
TM
2005 Re-introduction of CATnap
TM
Driven by new emphasis on safety and unit economics
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Commercial Experience
Over 200 million pounds of catalyst in over
200 applications
31 applications in North America
All catalyst unloaded (dump and/ or
vacuum) under air
No incidents of catalyst pyrophorics
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Reduce feed rate and unit temperatures
Introduce carrier oil, flush out process oil and
establish oil recycle
Inject CATnap
TM
passivating chemical at feed pump
Circulate chemical and continue cooling to 280 F
Discontinue circulation and de-oil unit
Cool and purge with nitrogen to remove hydrogen
and hydrocarbon vapor
Introduce dry air flow to remove catalyst by
dumping or vacuuming
Shutdown Procedure
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Unit Shutdown
Temperature during Shutdown
200
300
400
500
600
700
0 5 10 15 20
Time, hr
T
e
m
p
e
r
a
t
u
r
e
,

F
Reactor Inl et
Bed 1 Outl et
Bed 3 Outl et
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Unit Shutdown
Viscosity during Shutdown
10
12
14
16
18
20
22
24
26
0 5 10 15 20
Time, Hr
V
i
s
c
o
s
i
t
y
,

c
S
t

@

1
2
2

F
Feed
Product
Start chemical
injection
Injection complete
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Results
Safety
All catalyst was unloaded under air
Eliminated catalyst self-heating and pyrophorics
characteristics
Slight heating in bottom of bottom bed due to air
leaking
Eliminated dust emissions
Time savings
Faster shutdown procedure no hot H
2
strip
No delays for dust or pyrophorics
Permitting procedure was simplified
Unloaded catalyst faster than previous changeout
utilizing inert entry
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Results
Cost savings
Reduced time to shut down unit and unload
catalyst
No nitrogen required for inert entry operations
Intangibles
Reduced concern of entry operations by
technicians and refinery personnel
Improved quality and productivity
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Concerns
Reactor reached embrittlement temperature
May be due to faulty thermocouples
Unit was de-oiled at low pressure
Catalyst had some oilyareas
May be improved with better de-oiling procedure
Heating of catalyst in bottom bed
Likely due to valve not fully closed
Oil in reactor
Residual oil film removed by hydro blasting
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Conclusions
CATnap
TM
application was a success
Passivation offers a viable alternative to
inert entry operations
Offers possibility to largely eliminate what
is commonly believed to be the most
dangerous activity in petroleum refineries
CATnap
TM
technology is being evaluated for
other BP operating units
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Questions and Answers