Problematic Low-Temperature Shift

Catalyst Reduction

A charge of low-temperature shift catalyst does not have to be reduced often in modern ammonia
plants. Unfamiliarity with rarely used equipment caused a potentially dangerous temperature
runaway. Prompt action alleviated the problem and allowed the catalyst to operate efficiently for the
next 7 months, even though it had been severely overheated. An error during the delicate operation of
reducing a charge of low-temperature shift catalyst can cause costly damage to the expensive
catalysts.

I.R. Barton
ICI Katalco, Billingham, Cleveland T523 1L8, England

introduction upstream of a main bed, the guard reactor life has typi-
cally been extended from a few months to almost two
years while providing protection from poisoning for

S
ince the early 1960s most ammonia plants have
operated with one or more low-temperature shift
(LTS) reactors. This process step considerably
lowers the carbon monoxide content of the synthesis
gas and produces extra hydrogen. This means that
complex carbon monoxide removal systems can be
replaced with a simple methanator, significantly low-
ering cost and improving efficiency.
The addition of the LTS reactor in commercial
ammonia plants was made possible by the develop-
ment of a copper catalyst. Early LTS catalysts were
very susceptible to poisoning and generally achieved
lives of less than one year. This meant that installing
and commissioning a new charge of LTS catalyst was
relatively routine. Over the last 30 years considerable
improvements have been made in LTS catalysts and
purification systems. These improvements have meant
that lives of the catalyst have been extended to 4 or 5
years if a single reactor is used. If a configuration is
used where a small sacrificial guard reactor is placed
the main reactor.
With very few exceptions, modern LTS catalysts are
based on a formulation of copper, zinc and alumina. It
is the copper surface that provides the active sites for
the shift reaction. The catalysts are prepared as metal
oxides and so the copper oxide must be reduced to
metallic copper to activate the catalyst prior to use.
The reduction of copper oxide to metallic copper is
normally carried out with hydrogen. This reaction is
very exothermic, and a suitable means of removing
heat must be used to ensure that the catalyst is not
damaged by overheating.
H2-»Cu + H2O
AH = -81 kJmoH (-35 Btu Ib mol-1)
The above reaction is very slow below 150°C (300°F)
and is normally carried out between 170 and 230°C
(340 to 450°F). Temperatures above this range are

AMMONIA TECHNICAL MANUAL 111 1996

higher than most LTS catalysts see in normal opera-
tion and hence they tend to accelerate thermal deacti-
vation. This is a sintering process whereby the small
copper crystallites necessary to achieve a high catalyst
activity grow together, therefore decreasing the num-
ber of active sites.
At a temperature of 200°C (392°F), the heat released
by the above reaction is sufficient to raise the tempera-
ture of a typical LTS catalyst to 1,100°C (2,000°F) if it
were reduced in pure hydrogen. In practice the hydro-
gen is diluted by an inert gas, such as methane or
nitrogen, to such an extent that the inert gas carries
away the heat of reaction and maintains the tempera-
tures within an acceptable range.
It is possible to pre-reduce LTS catalyst prior to
shipping to the plant site and stabilize the material so
that it is safe to handle and load into a reactor. In prac-
tice this is rarely done as hydrogen for reduction can
normally be produced relatively easily on the ammo-
nia plant, and the LTS catalyst reduction is normally
incorporated into the overall plant startup.
Typical LTS Reduction
In a modem ammonia plant the reduction of the LTS
catalyst is normally carried out in one of two ways:
(a) By circulating a stream of nitrogen through a
reduction loop that contains a heater, the LTS reactor,
a cooler and separator to remove water produced in
the reduction, and a suitable compressor to recycle the
nitrogen carrier gas.
(b) By passing desulfurized natural gas once through
the LTS reactor before using the gas in the fuel sys-
tem, or, if this is not convenient, sending the gas to
vent.
Hydrogen for the reduction may be provided from
any convenient source, such as synthesis gas produced
with the LTS bypassed, gas from an adjacent plant or a
hydrogen-rich refinery off-gas. If such a source is not
available, hydrogen may have to be supplied from bot-
tles or tankers.
The catalyst reduction proceeds through three main
stages:
(1) Initial heating of the catalyst using the carrier gas
provides an opportunity to check instrumentation and
analysis systems.
AMMONIA TECHNICAL MANUAL
(2) Introduction of hydrogen to establish a suitable
exotherm in the catalyst. This is normally equivalent
to a hydrogen concentration of around 2 to 3%.
(3) Increase in hydrogen partial pressure and catalyst
temperature towards the end of the reduction to ensure
that all of the catalyst has been fully reduced.
The overall process normally takes between 8 and
48 h with the actual time being determined by the
quantity of copper in the catalyst which must be
reduced, the flow rate of carrier gas, the allowable cat-
alyst exotherm to prevent excess thermal sintering
and, occasionally, the availability of a sufficient flow
of hydrogen-rich reduction gas.
The exotherm generated by the heat of reduction can
be monitored by thermocouples positioned in the cata-
lyst as a temperature front moves through the reactor.
This provides a convenient way of checking progress.
A typical plot of various reactor temperatures taken
during the course of a catalyst reduction is given in
Figure 1. This plot shows the inlet temperature initial-
ly controlled at 210°C (410°F) by using a steam heater.
This inlet temperature is chosen to give a good rate of
catalyst heating. As the hydrogen is introduced, the
inlet temperature is lowered to allow a greater
exotherm, subject to the constraint that the maximum
temperature should not exceed 230°C (445°F). This
allows the hydrogen concentration to be increased and
Figure 1. Progress during typical LTS catalyst
reaction.
112 1996
the reduction to proceed more quickly. As the reduc-
tion reaction in each section of catalyst is completed,
the temperature falls to match the inlet temperature.
When the temperature in the lowest part of the reactor
begins to fall, the inlet temperature is carefully raised,
along with the hydrogen concentration, to confirm that
all of the catalyst is reduced.
The reduction of the LTS catalyst must be monitored
very carefully to ensure that an excessive concentra-
tion of hydrogen does not cause high temperatures in
the catalyst. Such an increase in hydrogen concentra-
tion can be caused by changes in the balance of the
inert gas system or changes in the hydrogen supply.
Any such changes must be immediately recognized
and appropriate action taken to ensure that high tem-
peratures do not result. Inlet hydrogen concentration
can be checked either by on-line plant analyzers, labo-
ratory analysis, or by using a specialized portable ana-
lyzer connected for the duration of the reduction.
A particular aspect of reductions that are undertaken
with natural gas as the carrier is the possibility of
cracking of heavier hydrocarbons that may be present
in the natural gas. This hydrocarbon cracking gener-
ates considerable quantities of heat and additional
hydrogen by the reactions:
If the temperatures in the catalyst are high enough to
initiate the above reactions, then the subsequent heat
release and hydrogen generation could result in an
uncontrolled exotherm. Such a temperature runaway
will certainly damage the LTS catalyst and may be
severe enough to threaten the vessel integrity. The
above reactions can be initiated at temperatures above
300°C (570°F) over a copper surface and so precau-
tions must be taken to ensure that such temperatures
are avoided if natural gas is used as the carrier.
Reductions that are carried out with nitrogen as the
carrier gas are inherently safer as there is no possibili-
ty of similar hydrocarbon cracking, although maloper-
ation that results in excessive hydrogen concentrations
or poor control of inlet temperature may still overheat
and damage the catalyst.
AMMONIA TECHNICAL MANUAL
Role of Catalyst Company Representative
At ICI Katalco, it is our policy to provide an engi-
neer with wide experience of LTS catalyst reductions
to be present, if practical and convenient for the plant
operator, whenever a charge of ICI Katalco LTS cata-
lyst is reduced. The role of the ICI Katalco engineer is
to assist during the reduction process by reviewing
operating procedures and contingency plans, offering
practical advice, monitoring progress during the
reduction and confirming that the catalyst has been
properly reduced prior to its use. The ICI Katalco
engineer is present only in an advisory or consulting
capacity for the plant operating personnel.
The ICI Katalco engineer will normally provide a
specialized portable gas Chromatograph which is cali-
brated specifically for the conditions seen in a reduc-
tion and can provide continuous hydrogen analysis at
the LTS reactor inlet and exit. This eases the burden
on the plant laboratory and provides rapid feedback to
assess the effect of changes in plant conditions.
Catalyst Reduction at AAF
P.T. Asean Aceh Fertilizers (AAF) operates a 1,000-
MTPD ammonia plant near Lhokseumawe at the north
end of Sumatra in Indonesia. The plant was started up
in 1984 and has a single unguarded LTS reactor. In
July 1994 the plant suffered an interruption in natural
gas supply due to a gas field pipe failure, and it was
decided to bring forward a planned shutdown. This
shutdown included changing the LTS catalyst which
had become poisoned after operating for 42 months.
During the shutdown, the LTS reactor was loaded with
56 m3 (1,980 ft*) of ICI Katalco Catalyst 83-3, a high
activity LTS catalyst, and topped with 6 m3 (210 ft3) of
ICI Katalco Catalyst 53-1, an older generation cata-
lyst. The volume of 6 m3 (210 ft3) represented the
amount of this catalyst that had been left in the ware-
house after the previous catalyst charging.
The new charge of LTS catalyst was to be reduced in
parallel with the startup of the rest of the plant, using a
once-through flow of natural gas as the carrier for the
reduction hydrogen. The natural gas contained approx-
imately 79% methane and 15% carbon dioxide with a
typical hydrocarbon tail of 5% ethane and 0.5%
113 1996
 'Rsdudon
CwrisfG«
Cootar
LJ t
Primary Secondary HTS LTS CO.
Rafennaf Rataiiw Rarowal
Figure 2. AAF LTS reduction circuit - natural gas.
propane. Hydrogen was supplied from the inlet to the
methanator and so the front-end of the plant (with the
LTS bypassed) had to be started up before the LTS cat-
alyst reduction could commence. See Figure 2 for the
configuration of the reduction system.
The carrier gas was taken from downstream of the
desulfurizer. A small recycle of hydrogen was used
from the methanator to the desulfurizer to ensure that
any organic sulfur compounds would be hydrogenated
over the cobalt-molybdenum catalyst. A second line
from the methanator was to be used specifically to
control the hydrogen for the LTS reduction. The inten-
tion of this system is to minimize the sulfur in the nat-
ural gas feed that could poison the reformer and the
LTS catalysts during the startup phase. However, the
complication of two hydrogen flows into the carrier
gas means that more care has to be taken to ensure that
excess hydrogen is not introduced into the system.
The natural gas flow was established and the LTS
reactor was gradually warmed up on the morning of
July 24, 1994. During this gradual warmup, which
took around 9 h, the sample lines to the temporary ICI
Katalco analyzer were purged and inlet and exit analy-
ses of hydrogen were 0.05%, due to the small amount
of recycle for feed desulfurization. These analyses
were confirmed by the laboratory.
AMMONIA TECHNICAL MANUAL
%CatefrstDecai
TM2 Tl-12 20
TH3 36
TM4 51
TI-1S 87
TUB 83
TI-68 99
OUT
Figure 3. AAF ammonia plant - thermocouple
positions in LTS reactor.
During the warmup phase, it was noticed that the
temperature at one of the thermocouples in the catalyst
was not behaving as expected. The first thermocouple
in the catalyst was reading lower values than the ther-
mocouple below it. The configuration of the LTS reac-
tor, which comprises the lower half of a combined
HTS/LTS vessel is such that the thermosheath is
inclined so that temperatures at different radial as well
as vertical positions are measured (Figure 3). The
positioning of the thermosheath may have caused the
first thermocouple to be too close to the vessel wall,
causing it to read low. The uncertainty about the accu-
racy of various measurements is not unusual in LTS
reductions, but it does inevitably contribute to confu-
sion if it is not certain which thermocouples can be
relied on.
The natural gas inlet temperature was raised to
200°C (392°F) to increase the rate of catalyst heating.
The natural gas flow rate was 16,000 Nm3/h (600
mscfh), equivalent to a space velocity of 260 h-1. In
order to speed up the process it was decided to
increase the natural gas flow to the maximum avail-
able, estimated to be around 18,000 Nm3/h (670
mscfh). At the same time, it was decided to increase
the desulfurization recycle to give a hydrogen concen-
tration of 0.5%. This would give better hydrogénation
114 1996
of any organic sulfur compounds and also provide an
initial level of hydrogen with which to start the reduc-
tion. These two decisions were taken independently by
different operators in the control room.
First Temperature Runaway
The first indication that something unusual was hap-
pening was when the control room operator noticed
that the natural gas flow had fallen quickly from
17,000 Nm3/h (635 mscfh) to only 8,000 Nirf/h (300
mscfh). The supervisor rushed outside to find an oper-
ator closing the carrier gas vent valve instead of open-
ing it. This mistake was quickly rectified and within 1
min the valve was fully opened and the flow increas-
ing at 13,000 Nm3/h (485 mscfh).
At the same time as the natural gas flow was cut, the
hydrogen recycle was being increased to achieve a tar-
get of 0.5%. With the low natural gas flow, the hydro-
gen concentration increased sharply. There was no
flowmeter on the hydrogen recycle and so it is diffi-
cult to estimate the actual hydrogen concentration.
The first sign of any problem in the catalyst was
when one of the thermocouples, Tl-13, positioned
36% of the way into the catalyst, increased rapidly
from 148 to 191°C (298 to 376°F). Clearly, the top
portion of the catalyst, which was being heated by nat-
ural gas at around 200°C (392°F), was hot enough to
initiate catalyst reduction. The thermocouple at the
20% point, Tl-12, showed a lower temperature, possi-
bly due to wall effects. At the same time, the portable
analyzer which was situated close to the LTS reactor,
registered a large increase in inlet hydrogen concentra-
tion.
With a sudden increase in temperature and the
known loss of natural gas flow, albeit for only a short
time, it was decided to isolate the hydrogen, stop the
natural gas flow, and vent the vessel. These changes
were accomplished quickly, however, the temperatures
in the reactor were rising rapidly and reached 580°C
(1,080°F) within 5 min.
Nitrogen was introduced at the top of the reactor,
however, the flow was less than 600 Nm3/h (22 mscfh)
and there was little immediate effect on the tempera-
tures.
20 min after the temporary cut in natural gas flow,
AMMONIA TECHNICAL MANUAL
the thermocouple situated at the 36% catalyst bed
depth was reading 740°C (1,364°F) and continuing to
rise slowly. With only a small flow in the reactor, the
temperatures lower in the catalyst showed less dramat-
ic change, rising from 145 to 225°C (293 to 437°F).
At this point, it was recognized that the flow of
nitrogen from the top of the reactor would push the
heat further into the catalyst bed and cause greater cat-
alyst damage. It was therefore recommended that the
flow of nitrogen be reversed and nitrogen vented from
the top of the vessel.
Soon afterwards the thermocouple at the 51% point,
Tl-14, peaked at 232°C (450°F) and began to fall, sug-
gesting that the heat was indeed being moved up the
vessel with the reverse flow.
During this time the upper thermocouple at the 20%
point, TI-I 2, had shown less increase than the 36%
thermocouple position, T1-Î3, with temperatures only
rising to 284°C (543°F). This cast some doubt on the
validity of Tl-13. The high temperatures were con-
firmed by inserting a temporary thermocouple into an
adapted pressure point at the 36% level - this thermo-
couple read 713°C (1,315°F). The measured tempera-
ture at Tl-13 peaked at 915°C (1,679°F), 7 h after the
initial excursion.
TM2-2K
1.800
U MO-
MOO'
TMS-SBH
S
TM4-51*
l'
TM8-8J«,
l
200- •400
10 20 30 40
Hours
Figure 4. AAF ammonia plant LTS catalyst
temperatures.
115 1996
Cooling of LTS Reactor and Catalyst
The rate of cooling, as measured by the fall at the
36% temperature point, TI-13, was very slow, due to
the low flow of nitrogen. Even when extra nitrogen
was made available, the cooling rate only increased to
15°C/h (27°F/h). The measured temperatures at the
various thermocouple positions are indicated in Figure
4.
The catalyst was left overnight to cool with reverse
flow of nitrogen and a meeting was held with the oper-
ations staff and the Katalco engineer to discuss the
options. At this meeting it was concluded that the tem-
perature runaway had been caused by cracking of
heavier hydrocarbons in the natural gas. The initial
temperature rise was due to a high hydrogen concen-
tration, however, the hydrogen recycle had been
quickly isolated and the total heat generated in the
reactor could not have been caused by the hydrogen
alone. The main focus of the discussions was to estab-
lish a safe way of cooling the catalyst and assessing
whether it was worth continuing with a reduction of
the lower portion of the catalyst or whether the whole
charge should be scrapped. If the catalyst had to be
scrapped, there would be serious repercussions, not
only in the costs of discharging and recharging cata-
lyst but also because a suitable replacement catalyst
would need to be delivered to Indonesia by air-freight
at great expense. Four options were considered:
(1) Continue cooling with reverse flow of nitrogen
until the temperatures were less than 300°C (572°F),
then resume with the normal high flow of natural gas
carrier. This was rejected as unsatisfactory as there
were likely to be hot sections of catalyst which would
not be easily cooled by the low nitrogen flow. When
the natural gas flow was resumed, these hot spots were
likely to cause more hydrocarbon cracking and anoth-
er temperature runaway.
(2) Use the air compressor to establish a forward
flow of nitrogen. This would give rapid cooling, but
the heat from the upper portion of the bed (which was
still at around 800°C (1,470°F)) would damage the
lower part of the catalyst.
(3) Use reverse cooling with steam. The potentially
high mass flow would give rapid cooling of the cata-
lyst. This was rejected by AAF who were concerned
about the effects of condensation in the bottom of the
AMMONIA TECHNICAL MANUAL
catalyst bed which had already been cooled by the
nitrogen.
(4) Modify the circulation route so that the air com-
pressor could pass a large flow of nitrogen upwards
through the catalyst. This was rejected by AAF who
were concerned that damaged catalyst may be blown
into the suction of the air compressor and cause some
machine problems.
With the above limited options available, it was
decided to continue with the low rate of cooling with
reverse flow nitrogen.
With the high temperatures seen in the catalyst, con-
cern was raised about the integrity of the vessel itself.
Checks by AAF confirmed that the vessel had not
been damaged. This was primarily due to the low
operating pressure and the short-term exposure to the
high temperatures.
After 60 h of cooling, the highest indicated tempera-
ture in the catalyst was 186°C (367°F) at Tl-12. The
LTS catalyst reduction had become the critical path for
restarting the plant and there was increasing business
pressure to make more rapid progress. It was therefore
decided to stop the nitrogen flow and proceed with the
reduction by restarting natural gas flow in the forward
direction.
Second Temperature Runaway
The natural gas was introduced very slowly over a
30 min period until a flow of around 6,000 Nm3/h
(220 mscfh) was established. The hydrogen recycle
was isolated and analysis confirmed the absence of
hydrogen in the feed. At this time the 20% thermocou-
ple (Tl-12) was falling slightly and the thermocouple
at the 36% position (TI-13) was rising slightly, indi-
cating that the hottest part of the catalyst was between
these two positions. The lower thermocouples began
rising more quickly. For over 40 min, the thermocou-
ple at the 51% point (Tl-14) rose from 163 to 188°C
(325 to 370°F). Over the next 2 min, it began to rise
very quickly, reaching 224°C (435°F). At this point,
the natural gas was isolated and reverse nitrogen flow
was again established.
As had been feared, there had clearly been enough
residual hot spots in the catalyst to cause more crack-
ing of the natural gas. Over the next 5 min, the catalyst
temperature rose to 446°C (835°F), before eventually
116 1996
peaking at 595°C (1,103°F). These temperatures were
measured at TI-14 at the 51% position in the catalyst.
The upper portion of the catalyst was evidently
already in the reduced state due to the hydrogen
released in the first runaway, and it showed little over-
heating during the second excursion. The second run-
away had caused overheating lower in the reactor and
increased the amount of catalyst that was damaged by
thermal sintering.
The second temperature runaway confirmed the fear
that the low nitrogen flow would not be adequate to
remove all hot spots in the catalyst that could poten-
tially trigger cracking of the natural gas. It was then
decided to use parts of the earlier options 3 and 4 as
follows:
(1) Cool the LTS with a high flow of nitrogen in a
reverse direction using the air compressor. This would
require approximately 24 h to modify the necessary
piping. The modifications were carefully studied to
ensure that they were safe and a screen was positioned
to make sure that no damaged catalyst was blown into
the compressor.
(2) During the time of the modifications steam
would be used for initial cooling. The higher mass
flow compared to the limited nitrogen would give
faster cooling and the risk of catalyst damage from
condensation was acceptably small due to the known
robustness of ICI Katalco Catalyst 83-3.
After adopting the above plan, the catalyst was suc-
cessfully cooled to around 100°C (210T) over a peri-
od of a few hours. Most of this cooling was accom-
plished using a high nitrogen flow.
Actual Catalyst Reduction
At this stage, the LTS reactor had suffered two major
temperature excursions during which the catalyst had
seen temperatures far in excess of those that would
cause major damage to the catalyst. Fortunately, quick
action by the operations staff to vent the vessel and
establish reverse flow of nitrogen had prevented all of
the catalyst being overheated. After the second excur-
sion, it was estimated that the lower section of the cat-
alyst had probably not been severely damaged by the
high temperatures and that this catalyst could provide
some useful shift activity, if it could be reduced suc-
AMMONIA TECHNICAL MANUAL
cessfully and if the damaged catalyst did not cause
high-pressure drop or uneven flows. This prognosis
was confirmed by computer simulations by ICI
Katalco of the expected performance of a small vol-
ume of active catalyst. Even if only the equivalent of
20 m3 (706 ft3) of undamaged catalyst remained at the
bottom of the reactor, it was calculated that this would
give acceptable performance at full plant rate for 12
months. After this time, the catalyst would become
poisoned and the CO slip would climb steeply.
During the period of cooling the pressure drop
through the catalyst bed was carefully checked and
compared to that expected for the unusual flow condi-
tions. This check showed that the pressure drop was
slightly less than expected, indicating that even though
the upper part of the catalyst was severely overheated
the physical integrity of the pellets had not been
affected. It was concluded that there had not been
much pellet breakage or agglomeration and so it was
felt that the lower portion of the catalyst could still be
used. This was confirmed by taking a sample of cata-
lyst from a pressure tapping in the vessel - the catalyst
sample had lost all shift activity due to thermal sinter-
ing, but the pellets were in good condition and very
strong.
After cooling with nitrogen all of the thermocouples
•' !
(392)
Inlet Hydrogen
Exit
HydfQQon
10 15 20 25 30
Hows
Figure 5. Eventual LTS catalyst reduction at AAF
(July 1994).
117 1996
in the catalyst registered less than 100°C (212°F). It
was then decided to proceed with a reduction using
nitrogen as the carrier rather than natural gas. As had
been clearly seen with the second temperature run-
away, it was possible for "hot spots" to remain in the
catalyst and these could cause hydrocarbon cracking if
natural gas were used as the carrier. The flow rate of
nitrogen was less than which could be achieved with
the natural gas and this, together with the lower heat
capacity of nitrogen, meant that the reduction would
take a little longer.
The reduction eventually proceeded with the nitro-
gen flow established in a forward direction. This
reduction was quite smooth and uneventful, and the
catalyst was determined to be completely reduced by
soaking with hydrogen. During the reduction, it was
clear that very little heat was produced by reduction of
the catalyst in the upper part of the bed. The upper part
of the catalyst showed some exotherm, but this only
lasted for an hour before the temperatures fell to
match the inlet temperature. The temperature profiles
are shown in Figure 5. This indicates that the catalyst
in the upper part of the reactor had already been
reduced to copper metal by the hydrogen released dur-
ing the temperature excursions.
225
(«n
Theoretical Profite with
220
£• («« 50* Catalyst Deactivated
Actual Measurements
215
feta Mm Z mond» «tor «tartHfj
<«9)
210
(«0)
205
(«1) •4
200
092)
20 40 60
Position in LTS Catalyst Bed % Depth
Figure 6. Actual temperature profile in AAF LTS
reactor.
AMMONIA TECHNICAL MANUAL
Subsequent Performance
The charge of LTS catalyst was eventually put into
service on August 3, 1994. The initial conditions
around the LTS reactor indicated that the performance
was normal, with an inlet temperature of 199°C
(390°F), an exit temperature of 216°C (421°F), a CO
slip of 0.12% and a pressure drop of 0.42 bar (6 psi).
A temperature profile taken from the reactor after 2
months operation is shown in Figure 6. This tempera-
ture profile is consistent with a theoretical profile that
is calculated for a catalyst bed that is fully deactivated
in the top half but which has normal activity in the
bottom hah0.
After operating for a couple of months, the CO slip
from the LTS began to increase. This was expected as
the remaining small volume of active catalyst began to
be affected by the levels of residual poisons in the syn-
thesis gas. The rate of increase of CO slip was consis-
tent with the projections based on an active volume of
20m3(706ft3).
The plant planned an overhaul in February 1995 to
complete major modifications that had not been possi-
ble during the unscheduled shutdown of July 1994.
This work included changing the ammonia converter
to an axial-radial configuration. As the LTS catalyst
was not expected to last for more than 12 months, it
was decided that this shutdown would be a convenient
time to replace the catalyst with new material.
The mixed charge of ICI Katalco Catalysts 53-1 and
83-3 was discharged in February 1995. The discharge
of the catalyst was straightforward with no agglomera-
tion of pellets or excessive dustiness. The pellets,
especially in the upper part of the reactor, were very
strong. Analysis of samples of the discharged material
confirmed that the catalyst had seen high temperatures
as indicated by low surface area measurements. The
discharged catalyst was found to be very strong with
some shrinkage caused by overheating.
Lessons Arising From Temperature
80 100 Excursions
Discussions between AAF and ICI Katalco yielded a
number of recommendations for future reductions of
LTS catalyst.
118 1996
 (1) The fundamental cause of the temperature run-
aways was found to be incorrect operation of the vent
valve on the natural gas carrier line. This valve is only
used infrequently and its unusual configuration with
the handle underneath the line increases the possibility
of it being turned the wrong way. The valve now car-
ries a warning to remind the operators of the danger of
incorrect operation.
(2) All actions associated with the catalyst reduction
will in the future be channeled through a single opera-
tor to ensure that changes are not carried out simulta-
neously. This will prevent the potentially dangerous
combination of a change in carrier gas flow and a
change in hydrogen flow.
(3) Natural gas carrier flow should be established
and stable before changes are made to the hydrogen
concentration. Sudden changes to the natural gas flow
would affect the hydrogen concentration and also the
temperature exiting the cooler that is positioned
upstream of the LTS reactor.
(4) The modified piping to allow reverse flow from
the air compressor upwards over the LTS catalyst
should be kept to provide an additional contingency
for future reductions.
(5) The positioning of the LTS thermocouple should
be reviewed to ensure that accurate and reliable tem-
peratures measurements can be obtained at all points
in the catalyst without being affected by the wall of
the vessel.
(6) If natural gas is used from the desulfurizer, it will
normally contain hydrogen. The hydrogen content
should be lowered to a minimum value during the
reduction. Consideration should be given to eliminat-
ing the hydrogen recycle during LTS catalyst reduc-
tion as the resultant sulfur poisoning will be negligible
and the control of the hydrogen content in the carrier
gas will be simpler.
DISCUSSION
Bob Prescott, Consultant: When the bed got to
900°C, you mentioned that you took steps to deter-
mine whether the vessel was damaged or not. Could
you elaborate on that a little? How was that avoided?
Barton: The steps that were taken consisted of check-
ing the surface temperature of the vessel and inserting
AMMONIA TECHNICAL MANUAL 119
Next Reduction
After the overhaul in February 1995. a fresh charge
of 56 m3 (1,980 ft») of ICI Katalco Catalyst 83-3 was
successfully reduced without incident. The catalyst
was reduced using nitrogen circulation through the air
compressor. This was because it was recognized that a
reduction in nitrogen is inherently safer than one with
natural gas. The slower reduction with nitrogen did
not cause any delay because the synthesis loop modifi-
cations meant that the reduction of the LTS catalyst
was not a critical path item.
Conclusion
The experience of the problematic LTS catalyst
reduction at the AAF ammonia plant serves as a
reminder of the serious consequences of a single
incorrect action during this procedure. Although the
plant had successfully carried out a number of LTS
reductions previously, the frequency of the reductions
is such that the operating personnel will often be unfa-
miliar with the details of this delicate process. Rapid
action by the operating team, together with timely
advice and strong support from ICI Katalco, prevented
the valuable charge of catalyst from being written off,
with serious consequences in plant downtime and
profitability.
This episode emphasizes the need for careful plan-
ning, complete with contingencies, and the value of an
experienced observer during the reduction of a charge
of low-temperature shift catalyst.
a probe into the catalyst through a pressure tap, and
checking the hardness on the outside of the vessel.
These tasks, together with the fact that the reduction
was done at very low pressure, were sufficient to con-
vince the operating team that the integrity of the ves-
sel had not been affected. Any other questions?
1996
Khan Said, ADV DIR Fertilizer: You have a nitrogen
source. Why didn't you use it instead of natural gas for
circulation?
Barton: Natural gas was used in the first place
because it can provide very effective means of doing
the reduction. I mention that hydrogen was used from
the methanator to provide the hydrogen for the
AMMONIA TECHNICAL MANUAL
reduction; hence, the rest of the plant was in the start-
up mode at the time. So, the plant really wanted to use
the air compressor to get the secondary reformer
going. It was therefore more convenient for them to
use natural gas. This is a very common practice at
many ammonia plants,
120 1996