Operating manual ammonia synthesis catalysts

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Contents

Page

Introduction 3

KATALCOTMJM 35-4, 35-8, S6-10 and S6-10R 4

KATALCOJM 74-1, 74-1R 5

Catalyst storage, handling and charging 6-9

Health and safety precautions 9-10

Start-up of KATALCOJM 35-4, S6-10 and 74-1 10-13

Activation of KATALCOJM 35-8, S6-10R and 74-1R 14

Operation 15-16

Shut-down 16

Catalyst discharging 16-18

Information contained in this publication or as otherwise supplied to Users is believed to be accurate and correct at
time of going to press, and is given in good faith, but it is for the User to satisfy itself of the suitability of the product
for its own particular purpose. Johnson Matthey plc (JM) gives no warranty as to the fitness of the Product for any
particular purpose and any implied warranty or condition (statutory or otherwise) is excluded except to the extent that
exclusion is prevented by law. JM accepts no liability for loss or damage (other than that arising from death or
personal injury caused by JM’s negligence or by a defective Product, if proved), resulting from reliance on this
information. Nothing here in should be considered to provide freedom to operate under any Patent.

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Introduction

This manual discusses the principles of start-up, operation and shut-down and the information
provided is sufficient for the preparation of the detailed operating instructions which of
necessity will be plant specific

The ammonia synthesis reaction, which is strongly exothermic, is one of the classic catalytic
reactions.

N2 + 3H2 ↔ 2NH3

The standard catalyst, which has remained more or less unchanged for over 80 years,
consists of iron with the addition of promoters and stabilizers, which increase its effectiveness
and stability.

Commercial ammonia synthesis catalysts are supplied as magnetite granules or in a pre-

reduced and stabilized form. Both forms need to be activated by reduction with either
synthesis gas or pure hydrogen before use. It is much more common to use synthesis gas for
the reduction because ammonia is produced at an early stage of the reduction and the heat of
reaction supplements the heat available from the start-up heater. Pre-reduced catalyst can
be commissioned much more quickly than the unreduced magnetite form. This both reduces
the time to full ammonia production and is used to control the quantity of aqua-ammonia
produced.

Most ammonia converters operate at pressures in the range 120-250 bar (1700-3600 psi),
which is a compromise between the equilibrium concentration of ammonia and compression
power/equipment cost. Under these conditions the recommended catalysts are
KATALCOJM 35-series and KATALCOJM S6-10. KATALCOJM 35-series was developed for
optimum performance at these pressures, whilst BASF developed KATALCOJM S6-10.
KATALCOJM S6-10 has been widely used for ammonia synthesis for many years and is now
exclusively available from Johnson Matthey Catalysts.

With the advent of low pressure synthesis technology Johnson Matthey Catalysts has
developed KATALCOJM 74-1 to maintain optimum performance at pressures as low as 80 bar
(1200 psi).

To produce ammonia, synthesis gas is circulated around the ammonia synthesis loop and
hence is contacted with the ammonia synthesis catalyst. Careful control of the temperature
profile in the catalyst beds is required to balance the equilibrium and kinetics of the ammonia
synthesis reaction. Temperature control within an ammonia converter is usually achieved by
using a number of adiabatic catalyst beds, with cooling between the beds provided either by
the addition of quench gas or by cooling within internal or external heat exchangers.

Alternatively, the catalyst can be cooled by the converter inlet gas passing through cooling
tubes within the catalyst bed.

As hydrogen and nitrogen react and are removed as ammonia from the circulating gas the
concentration of inert gasses, mainly argon and methane, increases. To keep the ‘inerts’ at a
reasonable level, part of the circulating gas is purged.

Ammonia produced by the process is condensed and recovered.

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KATALCOJM 35-4, 35-8, S6-10 and S6-10R

Johnson Matthey Catalysts supplies both unreduced and pre-reduced/stabilized catalysts.

Both types of catalyst are based on multi-promoted magnetite compositions and are available
in a range of granule sizes.

Composition KATALCOJM 35-4 and S6-10 multi-promoted magnetite

(AI2O3;K2O;CaO)

KATALCOJM 35-8 and S6-10R pre-reduced and stabilized

multi-promoted magnetite
(AI2O3;K2O;CaO)

From irregular granules

Nominal bulk density

Johnson Matthey Nominal size kg/m3 (lbs/ft3)
Catalysts size grade range (mm) 35-4 35-8
S6-10 S6-10R
A 1.5 – 3.0
C 3.0 – 6.0 2800 (175) 2200 (137)
E 6.0 – 10.0
G 14.0 – 20.0

Other sizes can be made to order

Johnson Matthey Catalysts ammonia synthesis catalysts can be used in all types of
converters. Magnetite must be reduced to metallic iron before use although
KATALCOJM 35-8 and S6-10R require only a brief activation period before operation. The
catalysts operate at temperatures in the range 350-550ºC (660-1020ºF) and at pressures of
100-600 bar (1450-8700 psi).

Catalyst density

The nominal bulk density figures are typical values only and this needs to be clearly
understood to ensure the correct quantity of catalyst is requested for a converter charge.

Due to the irregular shape of the catalyst it does not pack in a very uniform manner when it is
charged into a vessel. In order to ensure even flow distribution through the bed when in
service, particularly in radial flow beds, it is normal practice to vibrate the catalyst as part of
the charging procedure to give an even but higher bulk density throughout the bed. The
converter supplier should be consulted to determine the final bulk density to which the
catalyst should be charged. Often this is in the range 2650-3000 kg/m³ (175-187 lbs/ft3) for
unreduced catalyst and 2100-2500 (137-156 lbs/ft3) for pre-reduced variants. This needs to
be considered before an order is placed otherwise insufficient catalyst may be supplied.

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KATALCOJM 74-1 and 74-1R

Composition KATALCOJM 74-1 multi-promoted magnetite

(AI2O3;K2O;CaO:CoO)

KATALCOJM 74-1R pre-reduced and stabilized

multi-promoted magnetite
(AI2O3;K2O;CaO:CoO)

Form irregular granules

Nominal bulk density

Johnson Matthey Nominal size kg/m3 (lbs/ft3)
Catalysts size grade range (mm) 74-1 74-1R

A 1.5 – 3.0
B 3.0 – 4.5 2650(165) 2100 (131)
D 6.0 – 9.0

Other sizes can be made to order.

The magnetite in KATALCOJM 74-1 must be reduced to metallic iron before use. Typically
the catalyst operates at temperatures in the range 350-500ºC (660-930ºF) and at pressures
of 60-120 bar (870-1740 psi).

KATALCOJM 74-1 is used in low pressure ammonia synthesis plants.

Catalyst density

The nominal bulk density figures are typical values only and this needs to be clearly
understood to ensure the correct quantity of catalyst is requested for a converter charge.

Due to the irregular shape of the catalyst it does not pack in a very uniform manner when it is
charged into a vessel. In order to ensure even flow distribution through the bed when in
service, particularly in radial flow beds, it is normal practice to vibrate the catalyst as part of
the charging procedure to give an even but higher bulk density throughout the bed. The
converter supplier should be consulted to determine the final bulk density to which the
catalyst should be charged. Often this is in the range 2650-3000 kg/m³ (175-187 lbs/ft3) for
unreduced catalyst and 2100-2500 (137-156 lbs/ft3) for pre-reduced variants. This needs to
be considered before an order is placed otherwise insufficient catalyst may be supplied.

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Catalyst storage, handling and charging
Before charging, handling and discharging ammonia synthesis catalysts any potential risk to
health during these activities should be assessed and appropriate precautions taken. In
addition the Johnson Matthey Catalyst Handling brochure should be consulted.

Drum storage

Ammonia synthesis catalysts are generally supplied in mild steel drums having the following
packaging details. These parameters may change but precise information will be recorded in
the documentation covering the goods.

Catalyst Net weight

(Kg)
KATALCOJM 35-4 100
KATALCOJM 35-8 117
KATALCOJM S6-10 100
KATALCOJM S6-10R 117
KATALCOJM 74-1 100
KATALCOJM 74-1R 100

Drums must not be stacked on their sides or stacked more than four drums high, even when
held on pallets. Taller stacks tend to be unstable and there is the risk that the top drums may
fall off the stack, and the lower drums can be crushed due to the weight of the drums above
them. The metal drums are usually suitable for outside storage for a few months but should
be protected against rain and standing water. If prolonged storage is expected, they should
be kept under cover and away from damp walls and floors. The lids should be left on the
drums until just before the catalyst is to be charged. If the lids are removed it is important that
they should be replaced as soon as possible, so that contamination of the catalyst is avoided.
If the drum lid cannot be replaced, then the catalyst should be re-drummed without delay. If
any contamination occurs it is difficult to assess the extent of any damage without full
examination of the catalyst. If there is any doubt about the state of the catalyst it is best not to
charge it to the reactor.

Drum handling

Catalyst drums should be handled as carefully as possible. They must not be rolled. Catalyst
drums are often supplied on pallets, which reduces the likelihood of damage in transit, but
requires suitable fork-lift trucks and a paved area to handle the pallets. The fork-lift truck to
be used for unloading the pallets should be fitted with rim or body clamps to avoid damage to
the drums. The use of containers for either catalyst drums or palleted drums eases shipment
and further reduces the likelihood of damage in transit but, again, suitable fork-lift trucks must
be provided at the reception point. It is important not to use standard forks to lift the drums
under the rolling hoops, as damage to the drums and catalyst is almost inevitable.

Pre-charging checks

It is worth taking care to ensure that the ammonia converter is returned to service in first class
condition after a catalyst change, as maintenance around the converter is made difficult once
the catalyst is in its reduced state. Typical items worth considering are:

Check the catalyst support grid for integrity.

Check the cleanliness of internal heat exchangers. Fouling will reduce heat transfer efficiency
and reduce the converter efficiency.

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Check internal heat exchangers for leakage (possible bypassing). Johnson Matthey Catalysts
can provide information on the application of its TRACERCOTM Process Diagnostic
techniques on request.

Check quench valve operation.

Check thermocouple positioning and operation (warm each in turn and check corresponding
indication in the control room).

Ensure the vessel is dry before any catalyst is charged.

Clean any residual dust and debris from the catalyst beds prior to charging.

Charging ammonia converters

Ammonia converters should be charged with care following the recommended safety
precautions to ensure the task is safely completed. Due care and attention must be paid to
the loading technique to ensure a good gas distribution and high catalyst activity are
achieved.

1 Protective clothing

See the section regarding Health and Safety precautions. Operators handling the
catalyst should wear suitable safety equipment.

2 Handling pre-reduced catalyst

Pre-reduced catalyst is material that has been reduced and then stabilized by re-
oxidizing the outer surface of the catalyst particle. This outer layer prevents oxygen
reaching the reduced core of the particles and makes it possible to handle the product
safely providing sensible precautions are followed.

The catalyst should not be subjected to excessive vibration as this may break the oxide
skin and allow the reduced catalyst inside to react with air.

The catalyst should not be exposed to temperatures in excess of 50ºC (120ºF)in air as
this may lead to self-heating of the product as the reduced catalyst reacts with oxygen.
Note that the catalyst can achieve these temperatures if exposed to the tropical sun for
a few hours because it acts as a pseudo “black body”absorbing radiant heat and
thereby heating up the catalyst contained within the drum.

Avoid contact with water when charging the catalyst and ensure that it is not exposed to
rain. Moisture can lead to loss of the stabilization and allow exothermic oxidation to
occur.

During charging, the vessel thermocouples must be fitted and operational. The
temperature of the catalyst should be monitored throughout charging until boxed up and
under nitrogen.

A nitrogen supply together with a plan for applying a nitrogen blanket should be
available in case an exotherm occurs.

It is recommended that the vessel is charged from outside if possible. If it is necessary

to enter the vessel ventilation should be provided above the catalyst surface to ensure
that the atmosphere contains sufficient oxygen. Do not blow air through the catalyst
beds.

Manholes and vessel branches should only be opened when necessary as this can

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 lead to a chimney effect drawing air through the bed leading to self-heating.

The catalyst is screened prior to loading into drums; further screening is not necessary
and is not recommended because this could initiate self-heating.

During charging the catalyst should not be allowed to free fall more than 1 metre (3.3ft),
and should be carefully levelled and vibrated where necessary to ensure uniform gas
distribution.

All operators involved with charging pre-reduced catalyst should be aware of the safety
precautions required.

The converter should be boxed up and purged with nitrogen once charging is
completed.

Charging in dehumidified air has been used successfully in some applications.

3 Charging methods

All Johnson Matthey ammonia synthesis catalysts are irregular shaped granules and
due to the physical shape some differences in packing density are possible. Therefore
any charging method must ensure an even packing density across the converter beds
to gain the maximum benefit from the catalyst.

3.1. Multi-bed converters

Multi-bed converters can usually be charged using a hopper and tube allowing a
maximum free fall height of 3 metres (10ft) for standard catalyst and 1 metre (3.3ft)
for pre-reduced. The catalyst should be distributed evenly across the bed as it flows
in.

The bulk density must be checked regularly as charging proceeds. This is usually
achieved by comparing the charged weight with volume marks inside the vessel or a
volume calculated from dip measurements from the top of the vessel. Typically the
bulk density will be checked every 0.3 metres (1ft) in the early stages of charging
whilst the techniques are being established. Once consistent bulk densities are
being achieved the checks should be carried out at least every metre (3.3ft).

The bulk density can be adjusted by varying the catalyst free fall height or by
vibration to compact the bed. Care should be taken to ensure that the bulk density
across the bed is even so that process gas flow through the bed will be even.
Increasing the free fall height of the catalyst will increase the bulk density, whereas
reducing it will obviously have the reverse effect. The catalyst should be levelled
before vibration is started. Vibration is normally carried out using air driven concrete
vibrators for around 15-30 seconds and the whole area of the bed covered. The
length of vibration time should be varied until the correct bulk density is achieved.

Most converters are designed for bulk densities around 2800 kg/m³ (175 lb/ft3)
although it is possible for the charged density to vary from 2600 to 3000 kg/m³ (162
to 187 lbs/ft3) for oxidised catalysts. Bulk densities for pre-reduced catalysts are
lower, and a typical target density for these products is 2200 kg/m³ (137 lbs/ft3).

Walking on the catalyst should be avoided and where necessary appropriate

protection should be utilised such as snow shoes, or wooden planks should be used.

In order to ensure the catalyst is loaded in accordance with the converter supplier’s
intentions the supplier’s data should be consulted for any additional
recommendations or precautions.

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 3.2. Tube-cooled converters

Most tube-cooled converters can be charged by tipping the catalyst directly into the
converter once the tubes have been suitably masked to prevent catalyst ingress.
The tube spacer plates prevent excessive free fall of the catalyst.

The cooling tubes are normally plugged or covered in rows with a small channel
section and the catalyst hopper moved around the converter to provide an even
build-up of catalyst.

Health and safety precautions

Before charging, discharging and handling ammonia synthesis catalysts any potential risk to
health during these activities should be assessed and appropriate precautions taken.

Entry into inert gas atmosphere

Extreme care is needed during a shut-down when an entry has to be made into a vessel
containing an inert gas. Such atmospheres do not support life and personnel entering must
wear a suitable breathing apparatus. Failure to do so will result in loss of consciousness
within seconds of breathing the atmosphere followed within minutes by death. To avoid
accidental entry into the vessel, openings must be kept closed. When personnel have to work
inside the vessel prominent warning notices must be displayed. Everyone working within the
area should be made aware of the nature and dangers of asphyxia. They should know how
to effect a rescue and resuscitation of anyone who may be overcome. An integrated life-
support system is essential with adequate backup. If a company has no experience in such
activities then the work is often best done by a specialized service firm.

Discharged pyrophoric catalysts

Ammonia synthesis catalyst must be handled with great care when in the reduced state until it
has been fully stabilized as very high temperatures can be reached if uncontrolled oxidation is
allowed. Whilst still in the reduced state the catalysts must be kept separate from flammable
materials and handled in appropriate equipment such as closed metal drums, enclosed metal
skips etc. Air must not be allowed to flow through the reduced catalyst (e.g., by transporting
in open containers) as this can create a chimney effect and draw more air into the catalyst.

Stabilization is best carried out by slow oxidation of the catalyst. This is achieved by keeping
the catalyst wet and exposing it to air for a long period (several days) outside of the vessel.
The catalyst should be kept in a thin layer between 150 and 300 mm (6 and 12 inches) deep
to allow it to easily cool as self-heating can occur if the catalyst is dumped in heaps.
Hydrogen is evolved by the reaction with water and the area should be well ventilated.
Sources of ignition in and around this area should be identified and eliminated to prevent the
hydrogen evolved igniting.

Dust exposure

Short term exposure to the metals and metal oxides used in catalysts may give rise to
irritation of the skin, eyes and respiratory system. Over-exposure can give rise to more
serious effects. Material safety data sheets (MSDS) should be consulted for information.
Catalysts should be handled as far as possible in well-ventilated areas and in a way which
avoids the excessive formation of dust. Operators who handle catalyst must wear suitable
protective body clothing, gloves and goggles. Inhalation of dust should be avoided, and the

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appropriate occupational exposure limits should be strictly observed. If these limits are likely
to be exceeded, then respiratory protections should be used. Everyone involved in the
handling operation should clean up afterwards and, in particular, must wash before eating.
Clothing should be changed at the end of each shift, and more frequently if contamination is
heavy.

Ergonomics

Physical hazards arise from the handling of drums, materials and lifting equipment. Personnel
should be aware of these and take appropriate precautions.

Start-up of KATALCOJM 35-4, S6-10 and 74-1

Ammonia synthesis catalyst can be reduced either with synthesis gas (from downstream of
the methanator where this gas is free of oxygenates such as carbon oxides) or pure
hydrogen. Experience has shown that good results can be achieved after relatively rapid
reductions taking typically 3-4 days – at temperatures below 450ºC (840ºF) for
KATALCOJM 74-1 or below 500ºC (930ºF) for all other catalysts. The time taken to reduce a
charge of catalyst does however depend on the plant design and the limitations imposed by
ancillary equipment such as the start-up heater. The reduction procedure must avoid re-
oxidation of any part of the catalyst beds that have already been reduced. Some general
principles are outlined below, but Johnson Matthey Catalysts can provide detailed reduction
schedules to suit the individual requirements of a customer’s plant. When pre-reduced
catalyst is charged to the converter refer to page 14.

Water content

The water content of the gas entering the converter should be kept as low as possible
throughout the reduction, preferably less than 20 ppm v/v. This is helped by commissioning
the refrigeration system (if present) as soon as possible. Care must be taken when the
refrigeration system is brought on-line not to freeze the water generated from the catalyst in
the synthesis loop chillers. There is little risk of freezing once the ammonia content of the
water is about 20%. It is often possible to introduce ammonia into the synthesis loop to
increase the liquor strength before the reduction starts and until the catalyst is active enough
to generate ammonia itself. This allows the refrigeration compressor to run throughout the
reduction and minimize the water returned to the converter. (Pre-reduced catalyst in bed 1
will produce ammonia at a very early stage and minimize the potential problems with water
freezing).

Evolution of water from the reducing catalyst should be monitored in the converter exit stream
throughout the reduction. Experience has shown that a water concentration of 3000 ppm will
produce a high activity catalyst in a reasonable reduction time. The maximum allowable
water content in the effluent stream is 6000 ppm.

Gas rate

The highest possible gas rate should be used during the reduction procedure both to
minimize the reduction time and to ensure adequate gas distribution in the catalyst beds. The
gas rate is limited initially by the start-up heater capacity until heat can be recovered from
heat of reaction generated by the ammonia synthesis reaction in the reduced section of the
catalyst bed. This enables the gas rate to be increased quite rapidly after the first stage of
reduction for tube cooled converters.
Good gas distribution during reduction is particularly important because uneven flow through
the catalyst bed will give uneven reduction, and therefore uneven distribution of the ammonia
synthesis reaction during the reduction period. Catalyst that is reduced at a low flow rate will

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then be exposed to a higher water content than catalyst reduced at a higher flow rate. This
could lead to differences in catalyst activity. The damage caused by high water
concentrations is more severe at high temperature. If necessary, peak temperatures can be
decreased during reduction by lowering the operating pressure out of the loop.

Uneven flow can persist even with no mechanical imbalance in the system. The hotter parts
of the bed will offer more resistance to gas flow than the cooler parts and convection effects
can make the problem worse. Increasing the gas rate to the converter can rectify uneven
distribution. Higher flow rates give better distribution through the bed but require sufficient
heater capacity to maintain the necessary inlet temperature. Gas distribution problems will be
more significant in shallow very wide beds or radial flow converters: it is recommended that
pre-reduced catalyst is used in the first bed, especially for radial flow converters.

Reduction pressure

Reduction pressure has no effect on the final performance of the catalyst. Higher pressure
favours the ammonia synthesis reaction so that the heat of reaction can supplement the input
from the start-up heater and this can help control bed temperatures in the later stages of a
reduction. This is particularly useful with tube-cooled converters where the heat of reaction is
picked up by the inlet gas in the cooling tubes and then fed directly back to the catalyst bed.
With these plant designs the gas rate can be increased quite quickly following the initial
warm-up period. However, it is important that an even distribution of temperatures is
maintained. If there is any doubt about gas distribution or temperature measurement then
reduction at a pressure significantly lower than the intended operating pressure will make it
less likely that one side of the converter will get hotter than the other if the synthesis reaction
begins unevenly.

Start-up heater

Reduction pressure and gas flow rate are both limited by the heater performance and it is
important that plant operators know the limits of their heater design and have sufficient
instrumentation to ensure that these limits are not exceeded. Instruments, may, for example,
be designed for use at a different pressure and gas composition than those at the
commissioning period and correction factors should be made available before catalyst
reduction starts.

Typical reduction procedure for a multi-bed converter

This general procedure applies to the majority of modern converters with either axial or radial
flow, and with inter-bed cooling by either quench or heat exchange.

1 Bring the loop to the appropriate reduction pressure and establish a low purge
rate. The purge will ensure the circulating gas does not become too rich in
nitrogen as the hydrogen is removed by the reduction.

2 Start circulation round the loop and establish gas flow through the start-up heater
and the converter. With a fired heater there are generally two flow paths to the
catalyst: the normal route through the internal exchanger (the ‘main’ flow) and
also through the heater (the ‘heater’ flow) which joins the ‘main’ flow at the inlet to
the first catalyst bed.

3 Heat the catalyst at no more than 50ºC (90ºF)/hr to 350ºC (660ºF) for
KATALCOJM 35-4 and S6-10 and to 300ºC (570ºF) for KATALCOJM 74-1. The
gas rate should be as high as possible to assist heating. It is generally advisable
to begin heating with a relatively high flow of gas and then to decrease the rate
gradually depending on the time taken to reach the required temperature. Initial
catalyst reduction will typically start at 370-380ºC (700-720ºF), or 320ºC (610ºF)

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 for 74-1, although reduction may start at slightly lower temperatures. The water
concentration at the catalyst outlet should be checked as soon as the
temperature reaches 280ºC (540ºF) and measurements should continue as
frequently as possible until the reduction is complete.

4 Hold the temperature of the second and following beds at about 350ºC (660ºF)
for KATALCOJM 35-4 and S6-10, or 300ºC (570ºF) for 74-1 by control of quench
gas rates or heat exchanger bypasses as appropriate.

5 Decrease the heat-up rate to about 10ºC (18ºF) per hour, by increasing the gas
flow rather than by decreasing the heater output. Catalyst temperatures may fall
briefly as the gas rate is increased. If temperatures do not recover after a few
minutes decrease the gas rate until temperatures have risen by 10-20ºC (20-
35ºF) and then increase the rate again. If one side of the converter becomes
hotter than the other wait until the temperature differential decreases before
increasing the gas rate or the loop pressure. If necessary decrease the loop
pressure to limit the temperature of the hot part and then increase the reactor
inlet temperature to raise the temperature in the cold part of the converter.

6 As the temperature of the first bed rises check the water content of outlet gas and
keep it less than the operating limit of 3000 ppm, if necessary, by increasing the
‘main’ gas flow rate rather than by adjusting the heater output. Once reduction
begins at the inlet of the first bed the ammonia synthesis reaction will also start.
Heat of reaction will then increase the bed outlet temperature faster than the rate
at which the bed inlet temperature is being increased. This is called the ‘cross-
over’ point. The rate of increase of the outlet temperature should be controlled to
about 5ºC (9ºF) per hour by increasing the ‘main’ flow. At the same time it will
probably be necessary to increase the quench rate (or control flow through the
inter-bed heat exchanger) to keep the second bed inlet temperature at 350ºC
(660ºF) for KATALCOJM 35-4 and S6-10, or 300ºC (570ºF) for KATALCOJM 74-
1. The ‘cross-over’ temperature depends on the converter design but it is usually
about 400- 410ºC (750-770ºF).

7 When water evolution from the first bed decreases the second bed can be heated
and reduced in the same way as the first using quench (or heat exchange) to
keep the third and any following beds at about 350ºC (660ºF) for KATALCOJM
35-4 and S6-10, or 300ºC (570ºF) for KATALCOJM 74-1 if possible.

8 Reduce the third and following beds by exactly the same procedure remembering
to keep the temperature of all the unreduced beds at about 350ºC (660ºF) for
KATALCOJM 35-4 and S6-10, or 300ºC (570ºF) for KATALCOJM 74-1.

Temperature control during reduction

There are a number of potential problems with temperature control during reduction
depending on the design of each particular plant. Typical problem areas are:

a. Inadequate start-up heater sizing leading to difficulty in achieving the required

reduction temperature in the first bed.

b. It may be difficult to maintain the temperature of lower catalyst beds at the

recommended values by adding quench or by using heat exchanger
bypasses to keep the beds cool.

c. Sometimes the gas flow through the internal exchanger needs to be kept low
to achieve the desired catalyst temperatures and the high pressure shell and
/or the gas exit nozzle may then become hotter than is desirable.

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 d. In converters with interchangers it may be difficult to achieve a sufficiently
high reduction temperature in the final bed because gas from the upstream
beds will be cooled by the interchangers.

It is essential that plant operators know the equipment limits including the temperature limits
for the high pressure shell and the exit gas line, and have suitable instruments installed to
ensure that these limits are not exceeded. Where there are equipment limitations, Johnson
Matthey Catalysts can advise on the most appropriate catalysts and reduction procedures; for
example the use of pre-reduced catalyst or KATALCOJM 74-1 catalyst with its lower reduction
temperature may be the most effective solution.

Interruptions during reduction

If the reduction is interrupted by, for example, a circulator trip, a flow of gas must be
maintained through the catalyst to avoid backflow of water vapour through the already
reduced parts of the bed. A forward flow can usually be ensured if the purge valve is open as
suggested in step 1 of the reduction procedure (see pages 10-12).

Reduction in a tube-cooled ammonia converter

Reduction of catalyst in a tube-cooled converter follows the same procedure as above except
for the method of temperature control;

1 Once the reaction has started, control the water content of gas leaving the converter
to an operating limit of 3000 ppm by adjusting the rate of temperature increase.
Some cold quench may be needed at the bed inlet if the temperature rise cannot be
controlled just by increasing the gas rate – but quench should not be used until the
peak temperature exceeds 480ºC (900ºF) for KATALCOJM 35-4 and S6-10, or 430ºC
(810ºF) for KATALCOJM 74-1.

2 Maintain the peak catalyst temperature below 500ºC (930ºF) for KATALCOJM 35-4
and S6-10 or 450ºC (840ºF) for KATALCOJM 74-1 until reduction is complete.

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Activation of KATALCOJM 35-8, S6-10R and 74-1R

Ammonia synthesis catalysts can be pre-reduced and stabilized by controlled partial re-
oxidation to allow safe handling and charging to the converter. Pre-reduced catalysts require
a shorter activation period. When a complete charge of pre-reduced catalyst is used the
commissioning will only take about 24 hours. Alternatively, pre-reduced catalyst can be used
in the top one or two beds of a multi-bed converter or the upper part of a tube-cooled
converter. Part charges of pre-reduced catalyst simplify the early stages of an ordinary
reduction, which can often be difficult, by starting the ammonia synthesis reaction more
quickly.

These notes should be taken in conjunction with those for start-up of the conventional
oxidized catalysts.

There is no need to control water evolution during the activation of pre-reduced catalyst
because the concentration will be very low. The following steps should be followed when the
first bed of a multi-bed converter contains pre-reduced catalyst and the remaining beds
contain conventional oxidized catalyst.

1 Follow steps 1-2 of the typical reduction procedure for a multi-bed converter.
(see page 11).

2 Increase the bed temperature at not more than 50ºC (90ºF) per hour to 280-
300ºC (540-570ºF). At this temperature some reduction water may be observed
although the concentration will probably be less than 500 ppm.

3 Continue to increase bed temperature by about 10-20ºC (18-36ºF) per hour

regulating the temperature rise by increasing the ‘main’ flow. The second bed
temperature may also be increased at the same time providing that the outlet
water concentration is always less than 3000 ppm.

The third bed temperature should, however, still be controlled at 350ºC (660ºF)
for KATALCOJM 35-4 and S6-10, or 300ºC (570ºF) for KATALCOJM 74-1in the
usual way until the second bed reduction is completed.

4 The temperature ‘cross-over’ point in the first bed will probably be noted at about
400-410ºC (750-770ºF) as for ordinary catalyst. This temperature will however
be reached more quickly because significant ammonia formation will occur in the
top bed. Heat of reaction allows the gas rate to be increased at an earlier stage.
By this time there should also be a significant amount of reduction in the second
bed.

5 Continue the reduction of the second, third and any following beds by exactly the
same procedure as for oxidized catalyst remembering to keep the temperature of
all the unreduced beds at about 350ºC (660ºF) for KATALCOJM 35-4 and S6-10,
or 300ºC (570ºF) for KATALCOJM 74-1.

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Operation

Following initial reduction/activation the operation of conventional and pre-reduced catalysts

is identical and comments on operating procedure apply to both varieties.

Ammonia synthesis loops vary widely in design and detail, particularly for older plants.
Operating procedures can therefore differ from plant to plant. Some general principles do
however apply in all cases.

1 Higher catalyst temperatures give a closer approach to equilibrium but a lower

equilibrium ammonia concentration. As a catalyst ages, its performance can
usually be improved by operation at increased temperature to offset any
decrease in activity.

2 The lower the reduction and operating temperatures the higher will be the activity
of the catalyst. KATALCOJM 74-1 reduces at a lower temperature than other
ammonia synthesis catalysts, and this is a factor in enhancing its final activity. In
order to take maximum advantage of the high activity of KATALCOJM 74-1 it is
important to try and keep the reduction temperature lower than the final operating
temperature at all times, and to operate at as low a temperature as possible. In
this way the low temperature activity will be maintained for the maximum possible
time.

3 Ammonia synthesis catalysts deactivate slowly at temperatures higher than about

500ºC (930ºF), but at lower temperatures catalyst life is determined principally by
the concentration of impurities in inlet gas. The most serious catalyst poisons
are:

• Free and combined oxygen, usually in the form of CO, CO2 or water vapour

• Sulphur compounds which may originate from the feedgas although given
that the feed gas has been passed through the purification system and the
catalytic units downstream of the reformer this is an unlikely source of
poisons. Another source of sulphur is the lubricating oils used in the
compressors.

• Halogens

4 Methane and inert gases, mainly argon, which accumulate in the circulating gas,
decrease conversion by lowering the partial pressure of the reactants.

5 The equilibrium concentration of ammonia and the percentage conversion per

pass increase as operating pressure rises. At the same time however the power
required for the synthesis gas compressor also increases.

6 Higher circulation rates through the catalyst will increase the ammonia production
rate, but more power will be required for gas circulation and refrigeration.

Optimum loop operations must take all of these factors into account and respect any
mechanical limitations of the plant.

For a multi-bed converter determining the best operating temperature profile can be difficult.
If too much quench is reserved for the final bed the space velocity through the first bed may
be too low to make full use of the catalyst. The problem is then best solved by optimizing the
catalyst bed temperatures mathematically using computer methods. This is one of the
services Johnson Matthey Catalysts will provide for its customers by analysis of appropriate
plant data and subsequent optimisation of loop parameters. Catalyst activity usually changes
very slowly during the life of the converter so a check every six months is sufficient to

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maintain good operation. It is also possible to predict what adjustments will be necessary as
the catalyst activity declines.

With tube-cooled converters the catalyst temperature is controlled by the use of direct bypass
and/or interchanger bypass. This makes temperature adjustment fairly simple and best
results are obtained by running with the maximum cooling consistent with steady operation.
Automatic control of direct bypass is sometimes used. However, when temperatures are too
low there is a danger that reaction rates will become so slow that the converter cannot remain
autothermal. A useful procedure to avoid this is to drop the bed inlet temperature gradually
until converter temperatures begin to fall spontaneously and then to raise the inlet
temperature by 10ºC (18ºF). This will give stability during operational upsets such as poor
control of the hydrogen to nitrogen ratio. If the gas rate is kept constant during this procedure
ammonia production will slow down when the temperatures are too low and the converter
pressure or purge flowrate will begin to rise.

Whatever type of converter is used it is important that the appropriate hydrogen to nitrogen
ratio in the loop is maintained otherwise the excess reactant will have a similar effect to that of
inerts and decrease the conversion.

Because of the relative rates of hydrogen and nitrogen diffusion, the best results are often
obtained with a hydrogen to nitrogen ratio of about 2.8:1 at the converter inlet. The hydrogen
to nitrogen ratio in make-up gas will be almost exactly 3:1 in order to maintain the optimum
ratio in the loop. It is very important to control the flow of secondary air to give the correct
hydrogen to nitrogen ratio at the ammonia converter and not simply use the oxygen to adjust
the secondary reformer exit temperature.

Shut-down
An ammonia synthesis catalyst may be cooled with synthesis gas and left indefinitely without
loss of activity so long as poisons are excluded. When the catalyst is isolated with a nitrogen
atmosphere any moisture or oxygen impurity should be sufficiently low to avoid catalyst
oxidation. Nitrogen should normally contain less than 10 ppm oxygen. Nitrogen containing
higher oxygen levels than this can be used but care is required to limit the flow as much as
possible and to maintain the catalyst temperatures below 30ºC (86ºF).

Catalyst discharging
Ammonia synthesis catalyst is self-heating in the reduced state, therefore catalyst discharge
must be carried out in a controlled fashion with due regard to the safety procedures required.
There are several possibilities for discharging the catalyst.

• Hire a reputable specialist contractor and discharge the catalyst under an inert
atmosphere.

• Stabilize the catalysts with oxygen before discharge – great care is required and this
process should only be considered as a last resort.

• Drench the catalyst with water as it is gravity discharged maintaining a positive

pressure of nitrogen in the vessel at all times.

Discharge under an inert atmosphere using a specialist contractor

This is the recommended method for discharge because the contractor will have the specialist
knowledge and equipment to remove the catalyst safely. However appropriate safety

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measures must be strictly enforced (see page 8) during entry into vessels with an inert
atmosphere.

When the catalyst is removed from the converter it will still be self-heating and must be
handled very carefully until fully stabilized.

Stabilization in the converter

Stabilization tends to be a long procedure that cannot be guaranteed to oxidize all the catalyst
in the converter. There may still be pockets of catalyst remaining in the reduced state and the
discharge procedure must take account of this. Catalyst discharge must still be carried out
with precautions to ensure self-heating material is handled safely. Care must be taken to
ensure oxygen is admitted with good control and good gas distribution.

The following procedure gives a general outline of the steps required in stabilizing the
catalyst.

1 Cool the catalyst to less than 65ºC (150ºF) and purge the converter with nitrogen
containing less than 100 ppm oxygen.

2 Circulate nitrogen at the maximum rate possible through the converter at a

pressure in the region of 3-5 bar (43-73 psi). The pressure is not too important
but should be high enough to prevent air ingress into the circulating system. If
the synthesis gas or air compressor can be used to circulate nitrogen the
stabilization can generally be completed in 1-2 days. Keep the quench valves
tightly closed.

3 Carefully add air to the circulating nitrogen to give an oxygen content of 0.2-0.3%
inlet the converter. Keep the maximum bed temperature below 100ºC (212ºF).

4 An exotherm will pass through the beds as the reaction proceeds. Monitor the
oxygen content exit the converter as it will gradually rise to the inlet concentration
as the exotherm passes out of the catalyst.

5 After the exotherm has passed through, additional air is then slowly added to
raise the oxygen content to 20% over 15-20 hours whilst a maximum bed
temperature of 100ºC (212ºF) is maintained in the converter

6 The catalyst is held at 20% oxygen for approximately 5 hours and the converter
then cooled to less than 30ºC (86ºF) before circulation is stopped and the
converter discharge commenced.

Gravity discharge using water sprays

The layout of some converters allows gravity discharge of all the beds, however self-heating
catalyst cannot be simply run out into the floor. Unstabilized catalyst needs to be kept wet to
be handled safely; the catalyst is not stabilized by water however, and will become self-
heating again when it dries out. Note that hydrogen is evolved by the reaction with water and
can present a fire hazard. The catalyst discharge area should be well ventilated to ensure any
hydrogen can easily disperse.

If this method is adopted the converter must be kept under a small positive pressure of
nitrogen throughout to prevent air ingress reaching unstabilized catalyst in the converter.
Appropriate safety precautions must be enforced around the discharge port where nitrogen
may be present.

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The catalyst is normally run out onto a metal chute or conveyor with a continual fine water
spray playing onto the catalyst as it emerges. The catalyst then runs into a metal container.
The catalyst should be kept well wetted as steam from one part of the catalyst can pass to an
area which may have dried out and become hot, hydrogen will then be formed and ignite over
the hot catalyst.

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 © Johnson Matthey Group 2006
1097JM/0906/1/AMOG
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