Avoiding Syngas

Catalyst Mal-Operation
By
Gerard B. Hawkins
Managing Director, C.E.O.
Objective
This presentation covers frequent and costly
incidents related to catalysts mal-operation with
the focus of providing the plant operator with
recommendations to avoid plant outages and
catalyst losses.
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or by a defective Product, if proved), resulting from reliance on
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cannot be assumed.
Content
Review of incidents by reactor
Primary reforming
Secondary reforming
HTS
LTS
Methanator
Reactor loading
Support media
Some general comments on alternative actions when a
plant gets into abnormal operation
Reformer Catalyst Loading
UNIDENSE
TM
is now established as key to an even
reformer loading
However UNIDENSE requires some care to
achieve its full potential
A reformer in South America was loaded by an
inexperienced team and had to be unloaded and
reloaded with 20 % catalyst losses.
Lesson check experience of UNIDENSE loading
supervisors
UNIDENSE is a trademark of Yara International ASA
Reforming Burners Lighting
Lighting burners during start-up is a critical activity
The clear requirement is to increase the number of lit
burners as the plant rate is increased
and ensure the pattern of burners always gives an
even heat input
Obvious but was one component leading to this:
Reforming Burners Lighting
Lesson light only the number of burners you need at
each stage of start-up and keep the pattern/heat
generation even
Reformer - Carbon
Carbon deposition will occur when excess hydrocarbons
are introduced
There are several ways to do this:
Inadequate purging during a plant trip can lead to feed
being stored in the desulfurization vessel / pipe work
Then introducing nitrogen purge pushes this
hydrocarbon into the reformer
Naphtha fed plants have a high risk of feed condensing
and sitting in dead legs until some motive force pushes
this into the furnace
Erroneous feed flow measurement more critical in
low steam ratio plants
Reformer Carbon from Naphtha
Introduction of nitrogen during a start-up increased the
reformer pressure drop from 1.4 to 7 bar in 2 minutes
The nitrogen feed line was 100mm diameter and around
1km long, capable of holding up to 10te of naphtha
A spectacle plate was not swung during earlier operation
On previous occasions a drain valve was opened on the
nitrogen compressor this time the valve was not
operable
Reformer Naphtha in Dead Legs
Situation After Plant Trip

Steam to
Reformer
Flow
Feed CV
Feed ESDV
Steam to
Preheat
Coil
FM
Final ZnO
Bed
Feed
To Collector
or Flare
PCV
S Pt
Trapped Feed After Plant Trip
Reforming - Carbon from Liquid
HCs
A couple of ammonia plants in South America had
problems before the natural gas condensate removal
plant was installed
These plants took their feed off the bottom of the supply
line and hence took any liquids that were present
The liquid did not register in the flow meters which were
orifice plate type thereby reducing the actual steam to
feed ratio
Non-alkalized catalysts lasted as little as 6 weeks and
when replaced by alkalized products lasted a 2 year run
Reforming - Carbon from Liquid
HCs
Lessons
Gas flow meters largely ignore the presence
of condensed higher hydrocarbons
Note also that during startup flowmeters may
read in error if not compensated for
temperature and pressure
Alkalized reforming catalysts give very
significant additional margin against carbon
formation in primary reformers
Reforming Tube Failure from
Higher Hydrocarbons
A plant in North America was the sole user of gas that
came down a branch that went under a river
During a start-up after an extended shutdown - when
lighting burners liquid was seen flowing from a few
burners onto tubes
While the operator exited and radioed the control room
to shut off the fuel - a tube burst leading to significant
damage to the furnace/tubes
Reforming Tube Failure from
Higher Hydrocarbons
It was thought that hydrocarbons had
condensed in the cooler section of pipe under
the river
Lessons:
Consider potential for condensation of higher
hydrocarbons, especially
If lines are cooled below normal
If levels of higher hydrocarbons increase
Reforming Failure from
Condensation
We have another example of catalyst breakage
from condensation on start-up
A naphtha fed plant was not able to provide
nitrogen purge for the initial phase of start-up and
so heated the reformer using steam
Around 20 start-ups from cold eventually led to
breakage of catalyst, poor flow distribution, hot
spots and required catalyst change
Reforming Failure from
Condensation
Lesson:
Reforming catalyst should be warmed up to
50C above the dew point before introduction
of steam
Secondary Reforming
All incidents on secondary reformers are related
to the burners
The problem of increasing plant rate to the point
that there is inadequate mixing zone is well
understood but requires detailed CFD modelling
to predict
Secondary Burner Problems
Cost of Problems:
7-10 day
turnaround
Short Catalyst life
$52K/yr less than 10yr
Mechanical repairs
Estimated $65K/year
Poor mixing Burner failure
Bed damage Refractory damage
Secondary Burner Solution
Small flame cores
from all nozzles
No flame attachment
to rings
Good mixing of the
process gas and air
HTS
The main problem with HTS reactors is
upstream boiler leaks
We have another case where dehydration of the
catalyst has lead to an exotherm on startup
HTS - Boiler Leaks
This is a potential problem on ammonia plants with high pressure
boilers upstream of the HTS
Boiler leaks put stress onto the HTS catalyst by:
rapid wetting/drying and
pressure-drop build-up from accumulated boiler solids
These leaks are inevitable with steam pressures of 100bar
A serious leak will occur approximately every 12 years
Selecting a catalyst with high in-service strength significantly
improves probability of survival
HTS VSG-F101 Resists Boiler
Leaks
A plant in China suffered a complete
tube failure that tripped the plant
F101 was unaffected by this incident:
0
20
40
60
80
100
120
0.0 50.0 100.0 150.0
N
o
r
m
a
l
i
z
e
d

T
e
m
p
e
r
a
t
u
r
e
% Bed Depth
HTS - Dehydration
A plant in China had kept a charge of HTS catalyst in a spare reactor
for 1 year but had left this reactor open to the air so the catalyst
had adsorbed water
The start-up required nitrogen heating for 2 days to dry the whole bed
and in doing so dehydrated the catalyst in the top/bulk of the bed
100% steam was switched into the reactor against our advice of 5%
An exotherm started and then (unrelated) the plant tripped (site power
trip) which held the reactor with 100% steam
The exotherm reached 530C, and look several hours to cool down
with N
2
The final activity when on-line looked good, with expected low
pressure-drop.
HTS Lessons
Do not leave catalysts exposed to damp
atmospheres
VSG-F101 give the best survival of boiler leak
and over-reduction incidents
Incorporate the GBHE VULCAN Series
procedures when over-reduction is suspected
LTS
A plant in North America had to top skim its LTS
bed due to high pressure drop
The main cause was poor atomization of quench
water
This was not helped by the competitive catalyst
installed which developed very poor strength
when wetted
LTS
Lessons:
Ensure quench water nozzles are on the
shutdown inspection list
Check for adequate pipe length for
vaporization
Use catalyst with good strength after
wetting
Methanator
The main hazards when methanation reactors
are shutdown are nickel carbonyl (see plant
safety presentation on nickel Carbonyl) and self
heating when exposed to air
An example of self heating comes from a
methanator on an olefin cracker
Methanator self heating
The plant was shut down and purged with
nitrogen
The inlet and exit valves and thermocouples
were removed for repair
Open ends were covered in plastic sheet
Catalyst was in reduced state, with N
2
purge
Methanator Self-heating
A reading of 454C/850F was seen on re-
connection of the thermocouples
The plastic sheeting was not adequate isolation
Air entered the vessel and
A downward purge of nitrogen then gave a
reading of 649C/1200F on the bottom
thermocouple
Decided to change catalyst as needed 5 yr run
GBHE had product on site within 4 days
(including a weekend)
Methanator Learning
Reduced methanation catalyst becomes very hot
when exposed to air
Secure isolation/inert purge is essential for
maintenance on vessels containing reduced
catalyst
With little or no gas flow, thermocouples do not
show the peak temperature
Support Media
Dont spoil a ship for a few cents worth of tar!
Below Bed:
Support media does a key job preventing catalyst pass
through the exit collector and doing this with low
pressure-drop
Above Bed:
Support media placed on top of the bed protects
catalysts from high inlet gas velocities - which have the
potential to break catalysts through disturbance and
milling
High voidage media can also be used to reduce the
effects of boiler solid build-up
Support Media - problems
A plant decided to use some old support
balls that had been stored outside for some
years
This was a LTS duty so either alumina or
silica-alumina would be suitable
Shortly after start-up the reactor pressure-
drop started to increase
This eventually required a shutdown to
address
Support Media - problems
Investigation showed failure of the
support media
The catalyst had to be replaced
Cause is believed to have been rapid
drying of support that had got wet during
storage
Support Media use of Si/Al
Silica-alumina support is cheaper
A plant decided to use silica-alumina balls in a high
temperature shift bed
It was thought that this would be a low enough
temperature for silica migration not to be an issue
Not true silica migrated downstream and
collected on the tubes of the exchanger before the
LTS which required regular shutdowns to clean
A recent enquiry associated with HDS and HTS
catalysts simply specified ceramic balls
Support Media Catalyst
Protection
For the most severe duties, including
secondary reformers GBHE recommends
fused alumina lumps
High density
High strength
Inert (high purity alumina)
Difficult to blow around!
Support Media - advice
Lessons:
Store support media to the same standard as
catalysts the cost will be the same if they
fail!
Only use high purity alumina support above
300C in steam environments
Use GBHE A
2
ST for protection against
accumulation of boiler solids from boiler leaks
Use fused alumina lumps for the ultimate
protection against bed disturbance
A
2
ST Advanced Alumina Support Technology
Reactor loading
Dont be tempted to put that last bit in!
A methanol plant with a water cooled reactor experienced an
increasing pressure-drop on a new charge of catalyst
Eventually the plant had to be shut down
Inspection showed that catalyst had been loaded on top of
the tube-sheet as well as in the tubes
Removal of the catalyst on top of the reactor and 150mm
down the tubes restored the pressure-drop to normal
Reactor overloading
A hydrogen plant in Europe implemented a plant up-rate
and as part of this increased the HTS volume (we advised
it could be lowered)
In order to maximize the catalyst volume the hold-down
system was removed!
Milling then increased the pressure-drop
A reactor inlet distributor is better described as inlet gas
momentum destruction device
Lesson gas distribution/bed protection requires careful
design along with the rest of a plant up-rate
Reactor loading
A plant with a HTS reactor with two beds (one
vessel) went with a short load and split the short
load equally between each of the two beds.
The net effect was a bed L/D of 0.2 a long way
below the minimum recommendation of 1.0
The charge had to be replaced after 2 years
One can debate the merits of two beds with L/D
of 0.2 with gas mixing in-between or one bed with
an L/D of 0.4
The key is neither but to load the bed(s)
carefully:
Reactor Loading
The ideal catalyst loading method is by sock with
the minimum or raking
Any raking will introduce density differences that
will lead to early discharge of the catalyst due to
the uneven flow distribution produced
Lesson: allowing your loading company to rake
catalyst is equivalent to throwing catalyst away
Priorities When Things go Wrong
There is no universal advice but some
up-front thinking can lead to faster more
confident decisions
A number of incidents have involved
exotherms on catalysts which threatened
the integrity of their reactors
Example exotherm and action
Hydrogen was being removed from a process
stream using a copper oxide catalyst
During commissioning a hydrogen stream was
mistakenly introduced and the catalyst
temperature rose to 1000C
GBHE staff on site advised immediate
depressurization
Vessel damage was avoided
There were problems later on downstream mol
sieve driers from water produced which
accumulated in a dead leg
Depressurization vs Purging
With the previous example in mind it is
worth reflecting on the merits of
depressurization and purging
Depressurization
Several advantages:
It decreases the partial pressure of
reactants which may help slow the
temperature rise
It reduces the stress on equipment
enabling the handling of higher
temperatures
No motive force is required so it is
reliable
Lowering the pressure makes purging
more effective
Depressurization
Risks
Depressurization can generate high gas
velocities enough to fluidize catalyst beds
Fluidized catalyst beds can lose their top
protective layer (into the bed) and suffer:
flow distribution problems or
pressure drop increase if loss of the top layer
allows milling
Purging
Advantages
Can maintain plant pressure (but is
better if pressure reduced)
Fluidization risks to catalyst beds much
lower
Purging
Disadvantages
Difficult to achieve high flow-rates steam is
often the purge gas with highest availability
Steam can deactivate catalysts through
oxidation and in some cases sintering
Nitrogen is a good inert material but often
the available flow is limited
Need to consider trace oxygen in nitrogen
Ideal is nitrogen with enough hydrogen to ensure
reducing conditions
Conclusions
The incidents here suggest:
Selecting the right catalyst has a significant
impact on the ability of a plant to continue
operation through an unplanned event
Operator training/procedures are key to
avoiding incidents