The methanator is the last catalytic reactor in the gas preparation section of the ammonia plant.

Its main purpose is to remove the small amounts of carbon oxides (CO + CO2) which are
present in the process gas leaving the CO2 removal section.
Carbon oxides act as poisons for the ammonia synthesis catalyst and even small amounts of these
compounds will result in less activity/conversion in the ammonia converter.
Consequently the carbon oxides must be removed down to a level of a few ppm.
It is therefore important to ensure that the methanation catalyst is performing well.
The two methanation reactions are basically reverse steam reforming reactions.
CO + 3 H2
CH4 + H2O
CO2 + 4 H2
CH4 + 2 H2O
Both reactions consume hydrogen and it is therefore important to reduce the amount of carbon
oxides entering the methanator by operating the shift section and the CO2 removal section in an
optimal way.
The CO is converted rapidly in the top part of the methanator catalyst, whereas the conversion of
the CO2 proceeds much more slowly.
Reactions in middle and bottom of bed
In the lower part of the bed the gas contains mainly CO2 and very little CO.
CO2 + H2

CO + H2O

CO + 3H2

CH4 + H2O

Methanation of CO2 take place via reverse shift to CO.

Shift equilibrium predicts much more CO2 compared to CO.
(This depends on temperature and H2O content in feed).
CO partial pressure becomes very low and reaction rate becomes very slow.
The CO2 leakage will typically be 10 times higher than the CO-leakage
(also in case the feed contains no CO2).
Conclusion: A high catalyst activity is required in the bottom part of the

bed.

The methanation reactions are heat generating and each 1% of CO being converted results in a
temperature rise of 74C, whereas 1% of CO2 converted results in a temperature rise of 60C.
Under normal operating conditions the amount of CO + CO2 at the inlet of the methanator is in
the range 0.2-0.4% and as the outlet concentrations of CO + CO2 is only a few ppm with a
CO2/CO ratio of 5-10, a temperature increase of 15-30C in the methanator is seen.
CO + 3 H CH + H O (T =75C per % CO converted)
2

CO + 4H CH + 2H O (T =60C per % CO converted)

2

CO + H CO + H O (T = -15 C per % CO converted)

2

The two first reactions are reverse reforming reactions

The last reaction is reverse shift reaction
Reforming reactions both consume hydrogen and it is therefore important to reduce the amount
of carbon oxides entering the methanator by operating the shift section and the CO2 removal
section in an optimal way.
Under normal operating conditions the amount of CO + CO2 at the inlet of the methanator is in
the range 0.2-0.4% and as the outlet concentrations of CO + CO2 is only a few ppm with a
CO2/CO ratio of 5-10, a temperature increase of 15-30C in the methanator is seen.

Catalyst

PK-7R

Carrier

Al2O3

Active
Component
Shape
Size, Dia, mm

Ni
Ring
6

The methanation catalyst manufactured by Topse is a pre-reduced nickel based catalyst. The
carrier material is a special in-house manufactured alumina.
The carrier is impregnated with Ni using a special dispersion technique and afterwards the
catalyst is reduced at our in-house catalyst reduction facilities in order to obtain a high catalyst
activity.
Pre-reducing of the catalyst implies that it is able to operate at rather low temperatures providing
more flexibility in the daily operation, but also an important issue in plants where it is difficult to
achieve the normal methanator inlet temperature of around 290-300C.
The pressure drop across the PK-7R catalyst is low as it is supplied in the shape of a ring.
Furthermore, this shape has more void to accommodate any ingress of particles/chemical
substances such as carry-over from the CO2 removal section.
The process gas which leaves the LTS reactor is practically free of any poisons as these have
been absorbed by upstream catalysts. The methanation catalyst is therefore well protected against
most poisons which normally would deactivate a nickel-based catalyst, such as sulphur.
The potential poisoning which remains is the possibility of carry-over of various solutions from
the CO2 removal system and especially the potassium carbonate solution used in the Benfield,
Gianmarco Vetrocoke and the Catacarb process is regularly causing problems in industrial units
when it gets in contact with methanation catalyst. Small amounts of K2CO3 occurring during
daily operation are not a problem, but in case of carry-over of a major quantity, which could
happen due to a plant upset, the pressure drop in the catalyst bed will increase. In severe cases
the catalyst activity will also be affected due to K2CO3 deposits/crust formation.

Some CO2 removal processes has previously made use of an arsenic oxide and as arsenic is a
very strong poison for nickel catalysts. Ingress of such compounds will affect the performance of
the methanation catalyst.
The CO + CO2 leakage at the exit of the methanator should be analysed regularly (every shift) in
order to follow the performance of the catalyst closely. In most plants an on-line analyser is also
available and the results gained in the laboratory and on the analyser should be compared to
check the reliability of both types of analysis.
The pressure drop across the methanator should be logged and the development should be
evaluated by comparing with previous data.
Upsets in the frontend and/or the CO2 wash may cause high concentrations of CO and
CO2 to reach the methantion catalyst. This will cause a high temperature increase in the
methanator.
Exposure to high temperatures will cause the Ni crystal to sinter faster, causing an activity loss.
This is also called Thermal Ageing.
If the hotspot temperature tends to go above 450 C, the reactor should be bypassed. Besides
looking at the catalyst temperature, it is also important to keep the design temperature of the
vessel in mind, so that this is not exceeded.
The process gas which leaves the LTS reactor is practically free of any poisons as these have
been absorbed by upstream catalysts. The methanation catalyst is therefore well protected against
most poisons which normally would deactivate a nickel-based catalyst, such as sulphur.
Some CO2 removal processes has previously made use of an arsenic oxide and as arsenic is a
very strong poison for nickel catalysts. Ingress of such compounds will affect the performance of
the methanation catalyst.
Some catalyst manufacturer delivers unreduced methanation catalyst. It not possible to obtain the
same high activity as for a prereduced catalyst when reducing the catalyst on-site.
Operated correctly the methanation catalyst will be able to achieve long lifetimes. Most charges
in industrial operation will last 10-15 years and in some cases the catalyst change-out criteria is
the need for a mechanical inspection of the methanator vessel due to local regulations.
During the life of the catalyst the main operating parameter is the catalyst inlet temperature. It is
recommended to have a maximum of 2 ppm oxygen equivalents in the ammonia converter inlet
gas. One ppm of CO represents 1 oxygen equivalent and CO2 represents 2 oxygen equivalents.
In a gas having 1 ppm of CO and 0.5 ppm of CO2 we therefore have
1x1 + 0.5x2 =2 oxygen equivalents
which is close to the maximum recommended.
When the oxygen equivalents exceed the recommended level of 2 ppm, it is necessary to increase
the methanator inlet temperature by a few degrees and this should bring the CO + CO2 slip
down.

In case it is necessary to inspect the methanator without unloading the catalyst, the following
should be noted.
The methanation catalyst which has been in operation is pyrophoric and could heat up when
getting in contact with air.
Consequently, the catalyst should be cooled down before opening the reactor manholes.
It is considered good practice to inject nitrogen into the reactors when the manhole is open and to
only open one manhole in order to avoid chimney effects.
When handling nickel containing catalysts it is normally recommended to avoid contact with the
skin/respiratory system by using appropriate protective clothing.
The highly toxic nickel carbonyl, Ni(CO)4 is formed when CO from the process gas gets in
contact with the nickel contained in the catalyst. As long as the process gas does not get in
contact with the methanation catalyst at temperatures below 200C, the formation of nickel
carbonyl can be practically prevented. It is therefore recommended to stop the process gas to the
methanator before the inlet temperature reaches 200C and purge the vessel with nitrogen.
1.
Pressure-purge the reactor thoroughly (at least five times) with N2 before cooling. Purge
well above ground level during the depressurization steps.
2.
Reduce the pressure to slightly above atmospheric.
3.
Cool to ambient with continuous flow N2, vented well above ground level.
Nickel carbonyl can of course also be formed during start-up, and it is therefore advisable to
preheat the catalyst in nitrogen to about 200C before process gas is introduced. If a methanation
catalyst is operated in the region where nickel carbonyl is formed, the catalyst will obviously
slowly be depleted of nickel and therefore slowly lose its activity.