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Ammonia Production Sessions 1

1 mole of nitrogen react with 3 mole of hydrogen to produce 2 mole of


ammonia
Exothermic reaction (generate heat)
Nitrogen is produced from air and hydrogen is produced from natural gas (by
steam reforming)
N2 + 3H2 -> 2NH3 dH = -92.44 kJ/mol
Reversible reaction
Yield is increase as T decreases. Yield is increase as P increase (Le chatelier
principle)
Therefore we want low T and high P. But at low T, although high yield, but
product is produced slowly (low rate of reaction). What about P? Too high P is
impractical,

Ammonia Production Sessions 2

Desulphurisation where sulphur is removed from the process gas stream


Feed: desulphurised process gas
Steam is added to the feed stream upstream the primary reformer (heated to
about 500 degC)
Addition of steam is according to the steam carbon ratio
Methane and steam are passed thru a nickel catalyst in narrow tubes. The
tubes have a thick walls to withstand high T and P used in the reaction.
In primary reformer, natural gas (HC component) react with steam where H2,
CO and CO2 are produced. For example CH4 + H2O -> CO + H2 / CO + H2O
-> CO2 + H2
Primary reforming is endothermic: heat is supplied through burner in the
furnace box, where the burner surrounded tube in which required catalyst is
loaded and reaction take place.

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After that, process gas stream get into the secondary reformer which still
contain 13% methane that will be further reformed in the secondary reformer
(unreacted methane). Composition of outlet of primary reformer are
unconverted methane, H2O, CO, H2, CO2.
The 1st role of secondary reformer is to introduced nitrogen to the process
stream (for the synthesis of ammonia) where air is compressed by
compressor and that air is send to the secondary reformer. The 2 nd role of
secondary reformer is to further reformed the 13% unconverted methane.
Reaction in secondary reformer: Oxygen is removed where oxygen in air react
with some of hydrogen produced in primary reformer to produce steam (this
is called auto ignition combustion reaction) and this produce huge amount of
heat, T is raised to around 1000 degC. This will leave only nitrogen of the air
with some traces of argon. Second reaction: methane is further reformed by
the steam.
Methane slipped out from the secondary reformer is about 0.4 mole%.
The process gas exit the secondary reformer at 980 degC and pressure
around 35 bar. This stream is mainly made up of hydrogen, nitrogen, CO, CO2
and steam (also trace of methane).
No specific technology to capture CO, therefore need to convert CO to CO2
which will be absorbed in the CO2 removal unit.
Before entering HTS, the process gas high energy content is used to generate
a super heated steam (by the steam superheater heat exchanger). Therefore
the process gas entering the HTS reactor is cooled down to around 360 degC
thru a cooler.
In HTS: CO + H2O (steam) -> CO2 + H2, exothermic (therefore there will be
increase in the process gas temperature). As the conversion to CO2 increases
and the T increases, the rate of shift reaction decreases as the reaction
approaches equilibrium. The process gas is cooled in HX be4 entering LTS
reactor.
LTS operated at lower temperature than the HTS. Same shift reaction take
place. Almost all of the CO is shifted to CO2. Gas outlet the LTS contain about
0.3 mole% of CO.
Gas outlet the LTS is mainly hydrogen, nitrogen, CO2 and H2O with traces of
argon from air and some CO slipped from the shift reactor. The gas is then
cooled to allow all H2O in the stream to condense and separate upstream the
CO2 absorber.
CO2 removal: 2 columns which are CO2 absorber and CO2 stripper. CO2 is
absorbed by solution (such as 30% potassium carbonate). The rich solution is
stripped of from CO2 in the stripping column so that solution could be used in
recirculating manner to allow continuous removal of CO2 from the gas
stream. CO2 is removed from the stripper.
The gas exit from the absorber (in the top section of absorber) is mainly
hydrogen, nitrogen with 0.1 mole% of CO2, 0.3 mole% of CO and traces of
argon.
Since any O2 compound are harmful for ammonia synthesis catalyst, CO and
CO2 present in the process gas must be either be removed or converted to
another compound that is considered inert to the synthesis reaction catalyst.
This is why methanation reaction is utilized. CO and CO2 react with H2 in the

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process gas stream to produce CH4 and H2O. Methanation reaction is the
exact inverse of the primary reforming. It is exothermic and thus
accompanied by an increase in T.
Downstream the methanator, the gas is chilled to a temperature low enough
to allow for all the H2O produced during methanation to condense and
separate. Sometime molecular sieve adsorber is utilized to eliminate moisture
from the gas stream. Now the process gas mainly hydrogen and nitrogen with
traces of methane and argon is ready for ammonia synthesis (ratio of
nitrogen and hydrogen 1:3).
The gas is first compressed to the process required pressure then heated to
the required T in the inlet effluent HE where the gas outlet the ammonia
synthesis reactor heats up the gas inlet.
In the ammonia synthesis converter, N2 react with H2 to produce NH3. This
reaction is exothermic and thus proceed with an increase in T. The converted
gas is the cooled in the inlet effluent HE that we mention previously.
The reactor will has thick wall to withstand high P.
So the gas outlet the ammonia synthesis reactor is cooled and further chilled
to -33 degC in the refrigerant unit that utiutilizesmonia liquid as refrigerant.
The reaction is not 100% conversion reaction where there are unreacted H2
and N2 that is recycled back to ammonia synthesis loop once ammonia is
separated from the stream in the refrigeration unit.
Purge gas stream must be withdrawn to avoid the building up of inert in the
synthesis loop.
The produced ammonia is simply sent to a storage tank at -33 degC and at
atm P.

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Haldor Topsoe latest development in ammonia technology

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The pre reformed feed can be reheated to 650 degC before entering the primary
reformer. This will result in reduced firing in the primary reformer, and thereby a
reduced fuel consumption. When the hot flue gas is used to reheat the reformer
feed, the amount of heat available for HP steam production is reduced. This will
overall result in a reduced HP steam production in the ammonia plant. In general
the reformer size can be reduced up to 25% in a natural gas based plant by
incorporating a prereformer.
UHDE

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