Operating manual shift conversion catalysts

1098JM/0706/0/AMOG Page 1
Contents

Page

Introduction 3

High temperature shift catalysts 4

Low temperature shift catalysts 5

Isothermal & medium temperature shift catalysts 6

Catalyst storage, handling, charging and discharging 7

Health and safety precautions 10

Reduction and start-up of KATALCOTMJM 71-series catalysts 11

Operation of KATALCOJM 71-series catalysts 14

Reduction and start-up of KATALCOJM 83-3 catalysts 16

Operation of KATALCOJM 83-3 catalysts 20

Reduction, start-up and operation of KATALCOJM 83-5 23

(isothermal shift catalyst)

Reduction, start-up and operation of KATALCOJM 83-6 25

(medium temperature shift catalyst)

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 of shift converters.
The information provided should be used as the basis for the preparation of the detailed
operating instructions which of necessity will be plant-specific.

The water-gas shift reaction plays a major role in ammonia and hydrogen plant design and
operation. Good performance of the shift catalysts, and attainment of a close approach to
equilibrium and hence minimization of the CO slip from the catalyst system is critical to the
efficient and economic operation of the plant and ensures maximum hydrogen production
from the hydrocarbon feedstock. The water gas shift (or shift reaction) is highlighted below,

CO + H2O ↔ CO2 + H2 ∆H = -41.1 kJ/mol

The reaction is exothermic and high conversions are favoured by low temperature and high
steam to dry gas ratio.

Ammonia plants usually operate a two-stage system – a High Temperature Shift (HTS)
followed by a Low Temperature Shift (LTS) – with a suitable form of inter-bed cooling.

Hydrogen plant designs feature a number of differing shift conversion sections. Commonly
there is a high temperature shift stage followed by a PSA unit to separate the product
hydrogen from other components. On occasions a medium temperature shift (MTS stage) is
used in preference to high temperature shift. On older hydrogen plants, a two-stage system
is often utilized in which a HTS is followed by a LTS stage with suitable inter-bed cooling.

Modern catalysts for the high temperature shift stage operate typically in the temperature
range 300-450oC (570-840oF). The lower end of the range is determined by the design and
age of the plant; newer plant designs have led to lower inlet temperatures to take advantage
of advancing catalyst technology. The upper end of this range is based on the outlet
temperature of the older designs.

Corresponding operating temperatures for the low temperature shift section are 180-270oC
(355-520oF). .

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High temperature shift catalysts
Johnson Matthey Catalysts supplies its HTS catalyst in two forms, KATALCOJM 71-5 and
71-6 and in two sizes. The catalysts are formulated from iron oxide, chromia and copper
oxide, and provide efficient operation due to enhanced activity. The catalysts are also robust
at low steam to gas ratios.

Composition:

KATALCOJM 71-5M, 71-5 iron/chrome with copper promoter and

structural enhancer

KATALCOJM 71-6M, 71-6 iron/chrome with copper promoter and

structural enhancer

Physical properties (typical)

Catalyst KATALCOJM KATALCOJM KATALCOJM KATALCOJM

71-5M 71-5 71-6M 71-6
Form cylindrical cylindrical cylindrical cylindrical
pellets pellets pellets pellets
Length (mm) 3.6 4.9 3.4 4.7
Diameter (mm) 5.4 8.5 5.2 8.3
Typical loaded density
(kg/m3) 1220 1220 1250 1230
(lb/ft3) 76 76 78 77

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Low temperature shift catalysts
KATALCOJM 83-3 catalysts are based on copper oxide supported on a matrix of zinc oxide
and alumina. The established product, KATALCOJM 83-3 is also available in a smaller pellet
size designated KATALCOJM 83-3M, to allow optimization of performance and pressure drop.

Johnson Matthey also offers a premium product with the added benefits of low by-product
methanol formation and increased chloride resistance: KATALCOJM 83-3X. This is based on
the standard catalyst but is promoted with alkali oxides to minimize methanol by-product
formation. A smaller pellet size, KATALCOJM 83-3MX, is also available.

In all cases, the copper oxide must be reduced to its active metal state before use. This
critical step in catalyst activation is highly exothermic and the temperature of the bed must be
strictly controlled to ensure maximum catalyst activity. An inert gas such as natural gas or
nitrogen should be used to dilute the hydrogen used for the reduction reaction. All gases
used in the reduction must be free of catalyst poisons. The use of steam as an inert diluent
during reduction must be avoided as steam sinters the copper crystallites and therefore
deactivates the catalyst.

Composition:

KATALCOJM 83-3, 83-3M Copper oxide, zinc oxide, alumina

KATALCOJM 83-3X, 83-3MX Copper oxide, zinc oxide, alumina, alkali promoters

Physical properties (typical)

Catalyst KATALCOJM KATALCOJM KATALCOJM KATALCOJM

83-3M 83-3 83-3MX 83-3X
Form cylindrical cylindrical cylindrical cylindrical
pellets pellets pellets pellets
Length (mm) 3.2 3.0 3.2 3.0
Diameter (mm) 3.1 5.2 3.1 5.2
Typical loaded density
(kg/m3) 1360 1360 1360 1360
(lb/ft3) 85 85 85 85

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Isothermal & medium temperature shift catalysts
KATALCOJM 83-5 and KATALCOJM 83-6 are supplied as copper oxide supported on a matrix
of zinc oxide and alumina, and the formulations have been specially optimized to give stable
operation at higher temperatures than typical LTS catalysts. Before use, the catalysts must
be activated and the same considerations apply as outlined above. KATALCOJM 83-5 has
been specifically formulated for use in isothermal converters whereas KATALCOJM 83-6 is
formulated for use in adiabatic medium temperature converter designs.

Composition:

KATALCOJM 83-5, 83-6 copper oxide, zinc oxide, alumina

Physical properties (typical)

Catalyst KATALCOJM KATALCOJM KATALCOJM

83-5 83-5M 83-6
Form cylindrical pellets cylindrical pellets cylindrical pellets
Length (mm) 3.0 3.1 5.2
Diameter (mm) 5.2 3.1 5.4
Typical loaded density
(kg/m3) 1300 1300 1250
(lb/ft3) 81 81 78

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

Drum storage

Shift catalysts are generally supplied in mild steel drums, fitted with polythene liners, and
having the following packaging details. Precise information will be recorded in the
documentation covering the goods when supplied.

Catalyst Net weight (kg) Tare (kg) Drum packing

dimensions (cm)
KATALCOJM 71-5/M 220 18 88 x 59 x 59
KATALCOJM 71-6/M 220 18 88 x 59 x 59
KATALCOJM 83-3/M 240 18 88 x 59 x 59
KATALCOJM 83-3X/MX 240 18 88 x 59 x 59
KATALCOJM 83-5 220 18 88 x 59 x 59
KATALCOJM 83-6 220 18 88 x 59 x 59

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. 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 converter.

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 shipping containers for either catalyst drums or palleted drums eases
shipment and further reduces the likelihood of damage in transit. 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.

Johnson Matthey catalysts can also be supplied in Intermediate Bulk Containers (or IBCs) on
pallets. IBCs can be supplied in an Octobox. Typically an IBC will contain up to 1m3 (35ft3) of
catalyst.

Sieving catalyst

Shift catalysts are screened before they are packed into drums for dispatch, hence sieving on
site is not usually required, but in some instances attrition can occur in transit if the drums are
roughly handled. In this case some form of screening is advisable before charging, especially
if the catalyst appears to contain dust on delivery. Johnson Matthey should be consulted in
such situations. A good method of sieving is to pass the catalyst over a simple inclined

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screen. This is often the most satisfactory method, since vibrating screens can cause
additional unnecessary damage and loss. The screen should contain provision to collect the
dust, and at the same time avoid generating a dusty atmosphere. The mesh spacing should
be about half the smallest dimension of the catalyst pellet. While the catalyst is being poured
over the screen, the use of a vacuum system situated close to the sieve will control the dust
effectively.

Pre-charging checks

Before the catalyst is charged it is important that the condition of the catalyst support grid in
the converter and any supporting materials such as inert balls is checked. Any support or
hold down material in the HTS converter should be of a low silica type to prevent the
possibility of silica poisoning of the HTS catalyst. Some form of light metal shield or “spider”
fitted into the discharge manhole prevents an uncontrolled discharge of catalyst, when the
manhole cover is removed. The converter should be clean, dry and free from loose scale and
debris. It is important to ensure that the charging level is clearly defined, so as to avoid under
filling or overfilling. The desired level can be marked with chalk before charging is
commenced.

It is strongly recommended that the operation of the thermocouples is checked and their
position is noted to allow for temperature profile analysis during operation of the catalyst.
This can be done before charging is commenced by warming them in turn to ensure that the
correct indication is given on the instrument panel.

Charging the shift converter

The catalyst may be loaded directly from the drums or from intermediate bulk containers. The
general rules for charging catalysts into converters are:

• The catalysts should have a free fall of between 50 and 100 cm (20-40 inches) to
ensure a suitable packed density is achieved. (More than 100 cm/40 inches may
damage the catalyst)
• The catalyst must be distributed evenly as the bed is filled, with a maximum height
difference of 15 cm (6 inches) across the bed when completed.

Special procedures are required for loading tubular isothermal converters. Johnson Matthey
will advise on these procedures on request.

Discharge of high temperature shift catalyst

The catalyst is usually discharged from the converter with large mobile vacuum extraction
units. Occasionally it may be discharged by gravity flow from the bottom of the converter.

No special oxidation procedure is required before discharge. After cooling in steam the
catalyst is not pyrophoric although water hoses should be available in case the catalyst
overheats for any unexpected reason.

The normal shut-down procedure for inert discharge is as follows

1 Reduce pressure in the converter at a maximum rate of 1-2 bar (15-30 psi) per
minute, or as governed by the mechanical design of the equipment. Purge the
converter free of process gas with steam and cool to 150oC (300oF).

2 Replace steam with inert gas and cool to ambient temperature that is to say below
40°C (105°F)

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3 Discharge the catalyst under a positive pressure of inert gas.

Alternatively the procedure is as follows:

1 Reduce pressure in the converter at a maximum rate of 1-2 bar (15-30 psi) per
minute. Purge the converter free of process gas with steam and cool to 150oC
(300oF)

2 Replace steam with inert gas and cool to ambient temperature. That is to say below
40°C (105°F)

3 Fill converter with water and immediately drain off. Air can then be allowed to enter
the converter as required in order to achieve an atmosphere where the oxygen level
is high enough to support life, i.e. 21%.

Discharge of medium or low temperature shift catalyst

The catalyst is usually discharged from the converter with large mobile vacuum extraction
units or by gravity flow from the bottom of the converter.

Reduced MTS or LTS catalyst is pyrophoric and care must be taken when it is to be
discharged from the converter. The usual procedure is as follows:

1 Reduce the pressure in the converter at a maximum rate of 1-2 bar (15-30 psi) per
minute, or as governed by the mechanical design of the equipment.

2 Purge the converter with nitrogen and cool to less than 40oC (105oF).

3 Discharge the catalyst under a positive pressure of nitrogen. This may be done by
vacuum extraction or by gravity flow from the bottom of the converter. In the latter
case as catalyst falls from the bottom manhole it is sprayed with water, collected and
dumped on a suitable site where it is allowed to oxidize slowly.

In plants where there is insufficient available nitrogen for it to be used during catalyst
discharge then air must not be allowed to enter the converter when it contains reduced
catalyst otherwise gross or localized overheating will take place. In these situations it may be
convenient to fill the converter with water, drain and discharge the catalyst wet.

With this technique catalyst should not be allowed to sit in water for any length of time
otherwise catalyst breakdown can occur. Under these circumstances it is advisable to drain
the converter as soon as possible after filling to facilitate easy catalyst discharge.

Also note that when reduced catalyst is wetted hydrogen will be generated, hence it is
important that suitable precautions are taken to ensure an explosive atmosphere cannot
occur. This can be achieved by ensuring that the vessel is well ventilated by opening the top
man way. All sources of ignition around the converter must be controlled.

Special procedures are required for the discharge of tubular isothermal converters. Johnson
Matthey Catalysts will advise on the procedures on request.

Disposal of Discharged Catalyst

Through the CATALYST CARESM Programme Johnson Matthey Catalysts offers the
environmentally safe disposal of its complete product range.

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Health and safety precautions
Before charging, discharging and handling shift conversion catalysts any potential risk to
health during these activities should be assessed and appropriate precautions taken.

Entry into inert gas atmospheres

Extreme care is needed during a shut-down when an entry has to be made into a converter
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 of the converters, openings must be kept closed. When personnel have to
work inside the converter, 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 back-up. If a company has no
experience in such activities then the work is often best done by a specialized service firm.

Discharged pyrophoric catalysts

Catalysts discharged in the pyrophoric state must be kept separate from flammable materials.
Transport of such catalyst should only be in metal containers or metal-sided trucks. Dumps of
the catalyst should be within reach of water hoses so that any overheating that occurs can be
controlled. If pyrophoric catalysts are exposed to oxygen, then there will be an exotherm and
the size of the exotherm will depend on the concentration of oxygen in the gas being fed to
the converter. If the pyrophoric catalyst is left in heaps then high temperatures can develop
since the rate of heat release due to the oxidation is greater than the natural rate of heat
removal. It is therefore a prudent precaution to spread the catalyst thinly (150-300 mm) over
the ground until the oxidation is complete and under no circumstances should personnel be
allowed to walk over the catalyst until it has been fully stabilized. In order to test for this, the
temperature of the catalyst should be checked and compared against the ambient
temperature.

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 that
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
appropriate occupational exposure limits should be strictly observed. If these limits are likely
to be exceeded then respiratory protection 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, material and lifting equipment. Personnel
should be aware of these and appropriate precautions taken.

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Reduction and start-up of KATALCOJM 71-series catalysts

When the converter has been charged the high temperature shift catalyst must be reduced
before it can be used. The reduction of high temperature shift catalyst is invariably carried out
with process gas under conditions that allow the haematite to be converted to magnetite
without further reduction to metallic iron. Reduction also converts any of the small quantity of
residual hexavalent chromium (CrO3) to trivalent chromium (Cr2O3).

3Fe2O3 + H2 → 2 Fe3O4 + H2O ∆H = -16.3 kJ/mol

3Fe2O3 + CO → 2 Fe3O4 + CO2 ∆H = +24.8 kJ/mol
2CrO3 + 3H2 → Cr2O3 + 3H2O ∆H = -684.7 kJ/mol
2CrO3 + 3CO → Cr2O3 + 3CO2 ∆H = -808.2 kJ/mol

It is very important that steam should be present during the reduction procedure in order to
prevent over-reduction of the catalyst. It can be shown that if the H2O/H2 ratio exceeds 0.18
at 400oC (750oF) or 1.0 at 550oC (1020oF) then the desired magnetite is the stable phase.
Similarly, the CO2/CO ratio should exceed 1.16 at 400oC (750oF) or 1.0 at 550oC (1020oF).
The graph below summarizes the conditions necessary to prevent the reduction of Fe3O4 to
metallic iron in hydrogen and steam mixtures.

Figure 1. Minimum H2O to H2 ratio for HTS catalyst reduction

It should be noted that reductions are normally carried out at much lower temperatures,
typically starting at 320°C (610°F) and for some plants rising to 370°C (700°F) or more by the
end of the reduction process.

During catalyst reduction it is preferable to avoid the condensation of water in the catalyst
bed. If possible, the catalyst should therefore be heated in an inert gas stream to a
temperature that will prevent the condensation of steam before process gas is admitted to the
converter. It is suggested that the margin between the operating temperature and the
dewpoint be at least 20°C (36°F) to prevent condensation.

All HTS catalysts contain a small amount of residual sulphate that is converted to H2S during
the reduction procedure. The level of residual sulphur is so low in KATALCOJM 71-series,
that no special desulphurization step is usually needed. However, for some plants the
downstream operations such as the low temperature shift catalyst and / or the CO2 removal
system are sensitive to sulphur, and therefore it may be advisable to include an additional
desulphurization step during the start-up of the HTS catalyst.

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Reduction and start-up

In plants based on steam reforming of hydrocarbons no separate reduction procedure is

required for high temperature shift catalyst as the introduction of process gas serves to
activate, desulphurize and commission the catalyst bed. The commissioning of the HTS
catalyst can be performed in the following manner:

1. Purge the converter free of air with an inert gas and heat the catalyst above the
condensation temperature at a rate of about 50oC (90oF) per hour.

2. Care should be taken to ensure that the catalyst is not dried excessively prior to
reduction. This can occur if the catalyst is held in hot nitrogen circulation for an
excessive period (24 hrs+), for example if there are problems elsewhere in the plant
during start-up. When process steam is introduced to the dried oxidized catalyst, re-
hydration of the catalyst occurs and this leads to an exotherm, which can generate
temperatures in excess of 450oC (840oF).

To avoid this phenomenon, introduce process steam as soon as possible after the
catalyst is hot enough, or suspend nitrogen circulation whilst problems elsewhere are
attended to once the bed is up to temperature.

Should an exotherm occur when process steam is admitted, continue introducing steam
to remove the heat generated, and maintain the converter at low pressure. If excessive
drying is suspected, it is possible to rehydrate the catalyst by controlled addition of
steam, obviously monitoring temperatures carefully whilst small amounts of steam are
introduced.

It should be noted that this phenomenon only occurs on the initial start-up of the HTS
catalyst and does not occur on subsequent start-ups.

3. Establish a flow of process gas or steam through the converter at a wet gas space
velocity in the range 200-1000 h-1. Allow any water that does condense on the catalyst
to drain from the converter. KATALCOJM 71-series reduction will start at about 150oC
(300oF) if hydrogen is present and so process gas can be utilized at an early stage
during heating.

4. Increase the catalyst inlet temperature at a rate of 50oC (90oF) per hour until the bed
temperature reaches 300oC (570oF). Reduction will continue gradually until the normal
operating temperature is reached.

5. The high temperature shift reaction will gradually begin at temperatures in the range
300-320oC (570-610oF) and a temperature profile will develop through the bed. The
temperature rise will be about 13.5oC (24oF) for every 1% of carbon monoxide (in wet
process gas) that is converted. It is important, therefore, to restrict the amount of
carbon monoxide and/or the bed inlet temperature to prevent the bed outlet
temperature exceeding 500oC (930oF) during the reduction procedure.

6. KATALCOJM 71-series contains less than 0.025% w/w sulphur. Any residual sulphur in
the catalyst will be converted to hydrogen sulphide and removed during the normal
start-up as detailed above. It is therefore usual to bring the catalyst on line without the
need for a special desulphurization step. However, it may be prudent to check the
sulphur content in the outlet stream before bringing on line the LTS, if applicable. For
plants with downstream operations that are particularly sensitive to sulphur, an
additional desulphurization step can be employed. This consists of raising the inlet
temperature in the range 350-400oC (660-750oF), or at least as high as is achievable,
and then maintaining the catalyst bed at these temperatures for approximately 4 hours.
Monitoring of the sulphur content in the HTS outlet is recommended during this step.

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7. Increase the process gas rates and adjust bed inlet temperature to the start of run
operating value.

The above procedure is chosen as a reasonable compromise between energy use and stress
on the plant equipment. It should be used during the first reduction of a new catalyst in order
to avoid condensation on the catalyst, which can leach any soluble chromium (Vl) from the
catalyst, weakening its structure and reducing its life. During subsequent start-ups, plant
equipment permitting, normal process gas, or if not available then superheated steam, can be
used to warm up the catalyst from cold, and heating rates of 100-150oC/h (180-270oF/h) can
be employed without any detrimental effect to the catalyst. Greater care must be taken if the
catalyst has been wetted during the shut-down, and in this case the catalyst must be warmed
up slowly (at a rate of 50°C per hour (90oF/h)) at first to allow the pellets to dry out. Once the
bed temperature reaches the prevailing dewpoint, the bed should be maintained at this
temperature for approximately 4 hours to ensure complete dry-out of the catalyst. Once this
has been achieved, heating rates can be increased to 100-150oC/h (180-270oF/h).

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Operation of KATALCOJM 71-series catalysts
Plants that make hydrogen by steam reforming (whether an ammonia plant or a hydrogen
plant) usually incorporate a HTS stage followed either by a PSA unit or a LTS, CO2 removal
and methanation stages. Whatever the plant design, it is usual to operate the HTS catalyst to
give maximum carbon monoxide conversion. In plants with more than one shift converter, a
more flexible operation is possible and bed temperatures must be carefully optimized.
Optimum conditions can usually be determined by trial and error. When requested, Johnson
Matthey Catalysts will give advice based on calculations using its own specialized computer
programs for shift catalyst performance optimization.

The HTS converter is integrated with the process heat recovery system. It is usually
preceded by, and in many modern plants is also followed by, a waste heat boiler. The
flexibility of the HTS inlet temperature can therefore be limited by steam requirements and
boiler performance so that operation under optimum conditions will not always be possible.

The normal life of HTS catalysts in ammonia and hydrogen plants is 3-5 years although in
some cases it can be longer. End of life may be indicated by an increase in carbon monoxide
slip and by the end of the temperature profile moving towards and through the end of the bed.
It is normal practice, at the start of life, to take advantage of the high initial activity of these
catalysts by running at a low inlet temperature (around 300oC/570oF), although in some cases
this cannot be achieved due to limitations with the upstream or downstream heat recovery
requirements. As the catalyst ages and loses activity over its operational life, it is necessary
to raise the inlet temperature gradually to maintain the minimum CO slip, which corresponds
to the maximum CO conversion and maximum temperature rise across the bed. Over the life
of the catalyst, the inlet temperature would typically rise 30-40oC (54-72oF) depending on the
initial inlet bed temperature.

Catalyst operating life may also be shortened as a result of high pressure drop caused by the
accumulation of deposits on the top of the catalyst bed. In such cases it is possible to remove
these deposits by using a vacuum device during a convenient plant shut-down. If the
deposits are in the top section of the bed then this technique can be very effective, and an
extension of the operating life may be achieved. If the deposits have migrated down into the
main body of the bed, then vacuuming will be of limited use.

Loss of activity under normal conditions is usually caused by slow thermal sintering, in which
the small magnetite crystals agglomerate together in spite of the stabilizing effect of the
chromia. The larger magnetite crystals have a lower active surface area, and hence the
catalyst activity decreases. Greater rates of sintering are seen at higher temperatures. In
addition, the effects of certain poisons such as silica can reduce catalyst activity and life.

Temperature profile

Performance of the catalyst may be monitored during operation by the slope of the
temperature profile together with the corresponding increase of outlet carbon monoxide
concentration towards the end of life. The foot of the temperature profile will not move,
however, the gradient of the profile will slowly reduce due to catalyst sintering. A rapid
change in gradient indicates that there is an unusual problem. This may be due to deposition
of solids such as soda, silica, potash etc. from upstream equipment (such as a waste heat
boiler leak or high silica refractory), which block the bed and interfere with the gas flow. The
most common symptom of blockage is increasing pressure drop. If the plant rate is variable
then the analysis of the slope of the profile has to be suitably corrected for the variations in
plant rate.

Common problems can usually be identified from routine measurement of bed temperatures,
pressure drop through the bed and analysis of outlet carbon monoxide concentration. Advice
should be requested from your Johnson Matthey representative as soon as any unusual
conditions are experienced.

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Deposition of solids in the catalyst bed

If any solids are deposited on the top of the catalyst bed there will be an increase in pressure
drop across the bed. During a shut-down the bed can be skimmed by purging the reactor
with an inert gas and then vacuuming any contaminated catalyst together with the deposit
from the top of the bed. The pressure drop should return to a more normal value.

Caution: great care should be taken and procedures well defined before a person enters a
vessel containing an inert atmosphere.

Depending on the quantity of catalyst that has been contaminated by the deposit it may be
necessary to replace with an equivalent volume of new catalyst. No special reduction
procedure will be required for the new catalyst.

Sulphur

During use the catalyst will establish an equilibrium with any sulphur which is present in the
inlet gas. Any unexpected sulphur entering the converter will be retained by the catalyst as
iron sulphide and then slowly released as normal conditions are resumed. In steam reforming
flowsheets the inlet sulphur level should be much less than 1 ppm. However, a HTS catalyst
may be used downstream of coal-based or partial oxidation units where the sulphur levels
may be significantly higher. For concentrations of sulphur compounds less than 200 ppm in
the inlet gas there should generally be no significant effect on the catalyst. Above this level
bulk FeS will be formed which has only about half the activity of magnetite and allowance for
this must be made in the initial design calculations. Frequent cycling between sulphiding and
non-sulphiding conditions should be avoided, although the catalyst is strong enough to
withstand occasional cycling during plant mal-operation.

Johnson Matthey Catalysts can also offer KATALCOJM K8-11, a cobalt molybdenum catalyst,
which has been developed for shift conversion in a high sulphur environment. Details are
available from Johnson Matthey Catalysts.

Shut-down

During a short shut-down KATALCOJM 71-series may be left in an atmosphere of process

gas or steam at operating pressure and temperature. This can result in a partial oxidation of
the catalyst that will be reduced rapidly during restart.

If the converter is likely to cool during the shut-down period it should be purged with an inert
gas to prevent condensation of water. In addition the converter drains should be checked and
any accumulation of condensate within the converter drained off.

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Reduction and start-up of KATALCOJM 83-3 catalysts
LTS catalysts must be reduced with hydrogen before use. This procedure converts the stable
copper oxide component of the new catalyst into reactive copper metal. During reduction and
operation both the zinc oxide and alumina components are unchanged and act as a support
which stabilizes the copper metal crystallites, and also act as a reservoir for poisons.

CuO + H2 → Cu + H2O ∆H = -81 kJ/mol

Since the reaction is exothermic, the reduction procedure generates large quantities of heat
and relies on having equipment available to pass diluent inert gas through the LTS converter
to minimize the temperature rise.

The easiest procedure is to pass a continuous stream of inert gas, usually methane or
nitrogen, through the catalyst bed on a “once through” basis. Although this method can be
relatively expensive it has the advantage of allowing a high space velocity during reduction,
which will complete the procedure in about 12-24 hours. The alternative procedure is to
recycle inert gas, usually nitrogen, through the catalyst bed via a special reduction loop, which
also includes a recycle compressor and start-up heater. Space velocity will be limited by the
capacity of the recycle compressor but should preferably be at least 300 h-1.

Care should be taken to ensure that the inert carrier gas is free from reducing components
(such as hydrogen or CO) and oxidizing components (oxygen). In the event that natural gas
is used as the inert carrier the quantity of heavier hydrocarbons should be minimized as such
hydrocarbons can crack over copper catalysts. The carrier gas should also be free of catalyst
poisons such as sulphur or chloride.

With recycle systems there are several important points to remember

1 If the reformer is being used as the start-up heater, then carbon dioxide, evolved from
residual carbonates in the LTS catalyst, may methanate and the product methane
can crack on the nickel based reforming catalyst in the reformer and thereby deposit
carbon. There are various procedures to prevent this from happening and Johnson
Matthey can provide recommendations if required.

2 The concentration of hydrogen entering the LTS catalyst bed should not exceed 1.0%
v/v during the early stages of reduction in order to limit the temperature rise if un-
reacted hydrogen builds up in the recycle loop.

3 In some cases the “minimum gas density limit” (commonly referred to surging) of the
compressor may restrict the maximum hydrogen concentration in recycle gas during
the final stages of reduction.

4 Water evolved from the catalyst during reduction must be removed from the closed
recycle loop and not be recycled through the catalyst bed.

5 Hydrogen and nitrogen streams need to be free from water and oxygen that will
interfere with the reduction. Nitrogen should be free of hydrogen as this can lead to
excess hydrogen being fed to the catalyst.

Reduction procedure

The following reduction procedure is recommended for use in plants with facilities for either
“once-through” or “circulating recycle” systems for catalyst reduction.

1 Purge the converter with inert gas until all oxygen has been removed. Establish a
flow of inert gas and heat the catalyst bed to 120oC (250oF) at a rate of 50oC (90oF)
per hour or as governed by the mechanical design of the equipment. Any convenient
pressure, up to operating pressure, may be chosen for the catalyst reduction. In a

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circulating system a high pressure is normally preferred as it allows a higher gas flow
to be achieved in the system, and the higher partial pressure of hydrogen helps the
reduction.

2 Increase the inert gas flow rate to the maximum space velocity possible. Ensure that
both the hydrogen flowmeter and analyzer are operating satisfactorily as the
temperature approaches 130oC (265oF). Continue heating the catalyst until the top of
the bed is at 180oC (355oF). The temperature of the inert gas should not exceed
210oC (410oF) during the initial heating. If the inert gas space velocity is less than
300 h-1 more care is necessary as there can be poor gas distribution, which can lead
to localized overheating. Start recording bed temperatures during warm-up to confirm
that all the thermocouples are responding correctly and that the gas is well-distributed
through the bed.

3 When at least the top third of the catalyst bed has reached 160oC (320oF) hydrogen
should be introduced into the carrier gas entering the bed up to a maximum of 1.0%
v/v. Once the reduction reaction has started it will be necessary to record the
temperature at different points in the catalyst bed to determine the progress of the
temperature profile at regular time intervals. If the reduction reaction is slow with a
bed inlet temperature of 180oC (355oF) then the inlet temperature should be raised
cautiously to 190-200oC (375-390oF) and held steady at the temperature which gives
a satisfactory reduction rate.

4 Once reduction has started and a steady temperature profile has been established,
the hydrogen concentration should be increased. With nitrogen as carrier gas the
hydrogen concentration can be increased to 1.5% v/v and with natural gas as carrier
gas the hydrogen concentration may be increased to 2.0-2.5% v/v. The peak
temperature in the bed should not, however, exceed 230oC (445oF) and the hydrogen
concentration should be changed as necessary to control the temperature rise and
thereby limit the peak bed temperature. Once reduction has started it may be
possible to decrease the temperature of inlet gas entering the catalyst bed to 180oC
(355oF) or less. The temperature rise for 1% hydrogen is typically 30oC (54oF) in
nitrogen and 20oC (36oF) in natural gas.

5 As the reduction proceeds, the temperature profile will move down the catalyst bed.
The temperature rise will decrease when most of the copper oxide has been
converted to copper. At this point the catalyst bed inlet temperature may be raised to
200oC (390oF). The inlet hydrogen concentration can also be increased to 3-5% v/v
provided that the maximum temperature limit of 230oC (445oF) in the catalyst bed is
not exceeded.

6 When the catalyst reduction appears to be complete the catalyst bed inlet
temperature should be raised and held at 225-230oC (435-445oF) and then if
possible, the inlet hydrogen concentration in the inert gas should also be increased to
20% v/v. This holding state should be for a minimum of two hours. No temperature
rise should be observed and the maximum catalyst temperature should not exceed
230oC (445oF). Analysis should indicate that the hydrogen concentration inlet and
exit of the catalyst bed are within 0.2% of each other. If mal-distribution is suspected,
for example, if the space velocity is too low, then more attention should be paid to any
decrease in hydrogen concentration as; this may indicate that there is still unreduced
catalyst within the converter. Similarly, the temperatures throughout the converter
should be monitored to check for an exotherm, which again indicates the presence of
unreduced catalyst within the converter.

If an exotherm is observed during this soak period, then the hydrogen source should
be shut off immediately and the inlet temperature of the converter reduced such that
the peak temperature is reduced to less than 230°C (445°F). Once the peak
temperature is less than 190°C (375°F), the bed inlet temperature can be raised to
190°C (375°F) and the reduction restarted as per step 3 above.

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Under no circumstances should the gas flow to the bed be stopped since this is the
only means of ensuring that the exotherm can be reduced.

7 The catalyst reduction is complete and the converter should be commissioned.

Controlling the catalyst reduction

The reduction procedure has been designed to limit the temperature rise in the catalyst bed
by restricting the hydrogen concentration. This ensures that the maximum temperature in the
bed does not exceed 230oC (445oF) and the maximum catalyst activity is achieved. The
reduction reaction is indicated by the temperature profile which moves from the inlet to exit of
the catalyst bed at a rate which depends on inert gas space velocity, hydrogen concentration
and bed inlet temperature. The same principles also apply to radial flow beds.

During the whole of the reduction period it is important that operators should determine the
inlet and exit hydrogen concentration at regular intervals. The difference between these two
measurements during the time of the reduction represents the volume of hydrogen
consumed. Any oxygen present in carrier gas will also react with hydrogen to form water.
Normally the volume of hydrogen required for the reduction is 185 Nm3/m3 (195 scf/ft3) for
KATALCOJM 83-series catalysts. A comparison of the hydrogen consumed against the
theoretical consumption should be made as a cross check against the progress of the
reduction.

The volume of water forming during the reduction procedure will also provide an indication of
the progress. Measurement of water produced should only be used as an approximate check
on hydrogen uptake. KATALCOJM 83-series catalysts will produce 240 kg water/m3 (15 lb
water/ft3) catalyst, from the reduction process. Water formed from oxygen present in the inert
gas should not be included in any estimate.

Catalyst reduction is virtually completed when the inlet and outlet hydrogen concentrations
are the same and the whole bed is above a temperature of 225oC (435oF). The volume of
hydrogen consumed should confirm this. It may be difficult to achieve exactly equal hydrogen
concentrations at inlet and outlet of the bed and reduction may be considered complete when
the difference between the two measurements has been less than 0.2% v/v for more than four
hours.

Any complex copper-zinc basic carbonates present in the catalyst decompose during
reduction and release carbon dioxide. Carbon dioxide can be purged from the recycle system
but if for any reason the catalyst reduction procedure is halted, or the catalyst bed isolated at
reduction temperature, then any further carbon dioxide evolution will lead to an increase in
converter pressure. Pressure should therefore be monitored during the time that a converter
is isolated, when it contains partially or freshly reduced catalyst, and any increase in pressure
controlled by venting.

In addition, if the converter is to remain isolated for any length of time after the reduction is
completed but before it is commissioned, catalyst bed temperatures should be monitored
frequently. If any increase in temperature is detected the converter should be immediately
purged with inert gas to avoid any rapid temperature rise.

Hydrogen source

Almost any gas containing hydrogen is suitable for the reduction e.g. methanator gas, carbon
dioxide removal or high temperature shift converter effluent gas. Hydrogen should be free of
sulphur or chlorine and, if any carbon monoxide is present, allowance should be made for the
extra temperature rise during reduction.

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Natural gas

Natural gas is used as the inert carrier gas during reduction in many natural gas/steam
reforming plants. Any high molecular weight hydrocarbons in the natural gas can crack in the
pre-heater at temperatures as low as 300oC (570oF) to produce hydrogen. Most types of
natural gas have been safely used at a maximum catalyst temperature of up to 230oC
(445oF). It is therefore important that care should be taken in measuring the hydrogen
concentration carefully at the catalyst bed inlet and that the bed temperature is carefully
controlled to ensure the peak bed temperature does not exceed this value. Exceeding this
temperature can lead to side reactions occurring that can generate large exotherms.

Steam

Steam should never be used as the inert carrier gas during the reduction procedure. Use of
steam as a carrier will deactivate the catalyst and shorten the subsequent life of the charge.

Start-up

If the catalyst has already been reduced but is cold, the bed should be warmed to a
temperature above the dew point with inert gas before process gas is introduced to the
converter. During the initial start-up following reduction of the catalyst, the bed temperatures
will usually increase rapidly as the reaction comes to equilibrium with process conditions.

The peak temperature may reach 260oC (500oF) or higher at this stage but there will be no
damage to the catalyst because the peak will quickly pass through the bed. The high
temperature can be moved quickly through the bed by increasing the flow of process gas to
design rates as soon as possible. The catalyst bed inlet temperature should also be held as
low as possible provided that it is at least 20oC (36oF) above the dew point. For most duties
this corresponds to an inlet temperature of about 200oC (390oF). If there are particular
reasons for avoiding a temperature peak there are several ways by which it can be
minimized.

1 By increasing converter pressure to design level with inert gas before introducing
process gas.

2 Introducing process gas at low pressure while venting gas at the converter exit. This
is particularly easy after reducing catalyst with a ‘once-through’ flow of natural gas by
gradually replacing the flow of natural gas by process gas and then opening the inlet
and exit valves fully while closing the vent to commission the converter.

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Operation of KATALCOJM 83-3 catalysts
It is important to operate the LTS catalyst under optimum conditions to achieve the potential
savings in plant costs. The LTS catalyst is sensitive to changes in operating conditions but it
is not difficult to maintain fixed steam ratio, pressure and gas composition so that the only real
variable is the catalyst inlet temperature. During the commissioning procedure the bed inlet
temperature is gradually increased until the carbon monoxide concentration in exit gas falls to
the minimum level for the conditions. This is the optimum level for maximum CO conversion
and at higher inlet temperatures the carbon monoxide level will again increase. As the
catalyst ages or is poisoned it will be necessary to increase the inlet temperature to maintain
the minimum carbon monoxide concentration in the exit gas.

LTS catalysts often operate close to condensation conditions during the early part of the
catalyst life. To avoid condensation of water either in the catalyst pores or onto the bed the
inlet temperature should be at least 20oC (36oF) above the dew-point at all times. This may
mean that operation will be at temperatures higher than the optimum until catalyst activity has
fallen sufficiently for the actual and optimum operating temperatures to correspond. This is
not a problem because at temperatures in the range 200-205oC (390-400oF) the difference
between the equilibrium outlet carbon monoxide concentration and the optimum will be very
small and the actual outlet concentration will remain constant for a long period.

During the normal operating life of the catalyst, optimum operating conditions can be
maintained by a gradual increase of the bed inlet temperature as soon as the carbon
monoxide level increases slightly. Whenever changes in steam ratio or gas composition
occur the bed inlet should be checked to ensure that it is still at the optimum level. This
should be done by increasing or decreasing the bed inlet temperature by 2oC (4oF) and then
checking the carbon monoxide concentration at the bed outlet when conditions have
stabilized. If a decrease in the carbon monoxide concentration is detected the procedure is
repeated until the minimum level has been reached. A simple way of determining CO slip is
to observe the methanator temperature rise if the flowsheet features this converter. Minimum
CO slip from the low temperature shift will correspond to the minimum temperature rise
across the methanator.

Towards the end of the catalyst life the bed exit temperature may reach the maximum
allowable catalyst operating of 250oC (480oF). This is, however, a conservative figure and
short-term operation up to 270oC (520oF) is allowable although this will reduce the long term
catalyst activity.

At higher temperatures, however, the deactivation rate for partially poisoned catalyst is faster
and the carbon monoxide equilibrium level becomes increasingly unfavorable. Operation with
high outlet carbon monoxide concentrations will become increasingly expensive. It is usually
more economic to plan a catalyst change before the performance deteriorates beyond the
design level.

By-product formation

Methanol and, to a lesser extent amines (formed from methanol and nitrogen compounds
such as ammonia produced in the secondary reformer), are formed in low temperature shift
catalyst beds, particularly in the early stages of life when catalyst activity is at its maximum.
By-product formation is very sensitive to temperature and can be minimized by running with a
low inlet temperature. This is consistent with maximizing CO conversion. As ageing occurs,
by-product formation is reduced.

If operators require ultra-low methanol by-product formation, then KATALCOJM 83-3X or

KATALCOJM 83-3MX should be used.

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Temperature profile

The temperature profile through the catalyst bed is a useful indicator to follow changes in
catalyst activity especially when the outlet carbon monoxide concentration is at the
equilibrium level. For a fresh catalyst most of the reaction and the corresponding temperature
rise will be at the top of the bed. Loss of catalyst activity (or catalyst deactivation) during
operation is largely due to poisoning. Because the catalysts are “self-guarding” poisons
accumulate at the top of the catalyst bed. The temperature profile will therefore gradually
move from the inlet towards the exit of the catalyst bed as more poisons are absorbed.
Towards the end of the catalyst life when the reaction zone has reached the bottom of the
bed and the outlet carbon monoxide level has started to increase from the equilibrium
concentration, the catalyst should be changed.

Any variation from a typical temperature profile will indicate abnormal conditions.

1 A slow increase in bed temperature giving a flatter than average profile can indicate
that the whole catalyst bed has been partially deactivated. This may be due to the
presence of liquid water in the bed which would block the catalyst pores and wash
poisons from the top of the catalyst down to the middle or bottom levels. The catalyst
may also have been overheated.

2 If the temperature profile appears to be normal but the outlet carbon monoxide is
higher than expected then gas may be bypassing part of the catalyst bed.

Steam

The use of steam alone should be avoided as far as possible to prevent condensation of
water in the catalyst bed. During plant upsets, short periods of steaming may be unavoidable
but it is far better to isolate the low temperature shift converter and reduce pressure to
depress the dew point. The converter should then be purged with an inert gas.

Shut-down

During an extended plant shut-down, when the converter can cool down, process gas must
be purged from the converter to avoid the condensation of water on to the catalyst. This
could damage the catalyst by washing poisons from the top to the bottom part of the catalyst
bed on to fresh un-poisoned catalyst lower down the bed. Pressure should therefore be
decreased to atmospheric, before the temperature falls below the dew-point, and the
converter purged with an inert gas to remove all steam.

Catalyst poisons

Sulphur and chloride are the most serious poisons for LTS catalysts. Of the two, chlorides
are the more virulent, however, sulphur tends to be present in greater concentrations in the
process gas and therefore often determines the catalyst life.

Chlorine compounds are often present in process gas streams in extremely small
concentrations that cannot be detected by typical analytical procedures. The poisoning effect
is cumulative so that any concentration of chlorine in process gas will eventually poison the
catalyst bed and detection is only possible by the analysis of samples taken from discharged
catalyst.

The formulation of Johnson Matthey catalysts to provide thermally stable structures also
enhances the ability of these catalysts to absorb poisons. KATALCOJM 83-series catalysts
can absorb chlorides at the top of the bed and guard active catalyst in lower layers, and so
extend operating time. Strict attention is necessary however to maintain steam purity and to
avoid contamination of feedstocks or process air by chlorine compounds. Solvents containing

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chlorine should not be used for cleaning any items of plant equipment. If chloride poisoning is
an issue then the use of KATALCOJM 83-3X or MX should be considered as these catalysts
have a greater resistance to halide poisoning.

Sulphur compounds also affect the operation of KATALCOJM 83-series catalysts but are
much less virulent poisons than chlorine compounds. Johnson Matthey catalysts are self-
guarding against sulphur compounds provided that the typical levels found in ammonia or
hydrogen plants based on steam reforming are not exceeded for long periods.

Silica is also present in some process gas streams, for example by leaching from high silica
balls installed in the secondary reformer or HTS bed, and is absorbed by the catalyst bed and
gradually deactivates the catalyst. Small amounts of silica are deposited on the catalyst
surface but larger quantities react with the catalyst to form zinc silicate. Silica is not a typical
catalyst poison but has the effect of decreasing the catalyst’s capacity for other poisons and
therefore allows chlorine and sulphur to pass further into the catalyst bed.

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Reduction, start-up and operation of KATALCOJM 83-5
(isothermal shift catalyst)
KATALCOJM 83-5 is a member of the KATALCOJM 83-series of catalysts and many of the
same principles apply as for KATALCOJM 83-3 catalysts. KATALCOJM 83-5 is specifically
designed for use in isothermal (steam-raising) shift converters.

Before use the catalyst must be reduced with hydrogen in exactly the same way as for LTS
catalysts. The reduction is exothermic and must be controlled to prevent excessively high
temperatures and subsequent catalyst damage.

In an isothermal converter heat is rapidly removed from the catalyst and transferred to the
water-side circuit. Compared with the exotherm arising from a catalyst reduction in a typical
adiabatic shift converter, that observable in an “isothermal” shift converter is less marked.
However, a temperature peak is usually observable and its movement through the bed does
give some indication as to how the reduction is progressing. Furthermore, by observing
hydrogen concentrations inlet and exit the bed, as well as heat release/steam generation on
the water-side, good control of the reduction can be achieved.

Reduction procedure

The basic philosophy of the reduction is to warm up the catalyst in an inert atmosphere at a
steady rate to a temperature where reduction will start. Once this temperature is reached
hydrogen is carefully introduced at low concentrations to control the rate of reduction. As the
reduction proceeds the temperature and hydrogen concentration are steadily increased to
maintain the pace of the reduction without causing local overheating. Once reduction is
completed the converter is commissioned as normal.

Care should be taken to ensure the hydrogen content of the reduction gas is well controlled to
prevent excessive heat release that could cause problems with control of the steam
generation and lead to overheating of the catalyst bed.

If a recycle system is used the same points should be borne in mind as with the LTS around
potential carbon laydown in the primary reformer, hydrogen accumulation in the reduction
loop, minimum gas density and water evolution.

1 Purge the converter with an inert gas to remove oxygen. Establish a flow of inert gas
that is sufficient to ensure even gas distribution through the catalyst and heat the bed
at a rate of around 50oC (90oF) per hour. For this heating stage (and also for other
heating stages in this procedure), the pressure of the steam side, hence the
temperature has to be controlled in order to achieve the required temperature
changes.

The pressure in the catalyst bed can be any convenient value, higher pressures tend
to help the reduction by increasing the partial pressure of hydrogen.

2 Check the hydrogen analyzer and flowmeter are operating satisfactorily as the
temperature increases (before 130oC/265oF). During heat-up keep the inlet gas
temperature within about 30oC (55oF) of the catalyst bed temperature.

3 When the bed temperature has reached 160oC (320oF) hydrogen should be
introduced into the carrier gas at a concentration of 0.5-1.0% v/v inlet the bed.

4 Monitor the hydrogen concentration exit the bed and the steam raising on the boiler
side as indicators of the reduction rate. If no hydrogen is consumed and there is no
evidence of heat release cautiously increase the bed temperature towards 190-200oC
(375-390oF). Hold the temperature once a steady reduction rate is achieved.

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5 Once reduction has started the aim is to carry out the reduction at a steady rate by
adjusting hydrogen concentration and bed temperature.

In the early stages of reduction, once it has been established that reduction is under
way, the inlet hydrogen concentration can be increased to around 2.0% v/v. Keep
monitoring the bed temperatures, and ensure the temperature does not exceed
230oC (445oF).

6 As the reduction nears completion, the steam raising rate will reduce and the
hydrogen content exit the bed will rise towards the inlet concentration. The catalyst
temperature can then be steadily increased to 200oC (390oF) and then the hydrogen
concentration should be carefully increased to 5%.

7 Once the reduction appears to be finished a hydrogen “soak” is carried out to

complete the procedure. Raise the catalyst temperature to 225-230oC (435-445oF)
and then increase the hydrogen content to 20% v/v. This procedure should be
carried out steadily, monitoring the progress of the reduction closely and should take
a minimum of 2 hours. The hydrogen concentration exit the bed should be the same
as the inlet, indicating reduction is complete.

8 The catalyst is now reduced and the converter can be commissioned as required.

Start-up

The main problem during start-up is to prevent condensation on the catalyst. This is achieved
by heating the catalyst to a temperature of approximately 20oC above the dew-point (usually
by feeding steam into the steam side of the converter) before process gas is introduced.

Operation

The normal operating temperature for an isothermal shift converter is typically 240-260oC
(465-500oF) at inlet and exit of the bed although there will be a peak temperature of 280-
300°C (535-570°F) in the reaction zone.

The main mechanism for catalyst de-activation is poisoning. During the life of the catalyst
charge, the reaction zone will move slowly down the bed as catalyst at the top of the bed is
poisoned. In contrast to an adiabatic bed, the inlet temperature has very little effect on the
converter performance. Heat transfer in the converter ensures that the exit temperature is
usually close to the boiling water (steam) temperature, and the boiling temperature can be
adjusted to give the minimum CO slip. This is carried out on a trial and error basis by raising
or lowering the steam temperature by 2oC (4oF) and monitoring the CO slip.

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Reduction, start-up and operation of KATALCOJM 83-6
(medium temperature shift catalyst)
KATALCOJM 83-6 is also a member of the KATALCOJM 83-series of catalysts and is
specifically designed for use in adiabatic medium temperature shift (MTS) converters.

Reduction procedure

The reduction procedure is the same as that described earlier for the KATALCOJM 83-3 LTS
catalysts.

Start-up

The start-up considerations given for the KATALCOJM LTS catalysts also apply to
KATALCOJM 83-6.

Care should be taken to prevent condensation of steam on the catalyst during the start-up
procedure.

Operation

Introduction of process gas should follow the usual procedure for LTS catalysts. Normal
operating temperatures for KATALCOJM 83-6 are in the range 200-230oC (390-445oF) at bed
inlet. The inlet CO level for a MTS converter is higher than for a LTS converter and thus the
exit temperature will typically approach 300oC (570oF). The optimum inlet temperature must
be established on line by carefully adjusting the inlet temperature to establish the minimum
CO slip. In order to maintain the minimum CO slip, the inlet temperature will need adjustment
over the operational life of the catalyst, however, it is important that the exit temperature
should be controlled to a maximum of 350oC (660oF) otherwise the rate of deactivation
through thermal sintering will become unacceptably high.

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© Johnson Matthey Group 2006
1098JM/1006/0/AMOG
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