Ammonia Synthesis and Molecular Sieve

Ammonia Synthesis &
Molecular Sieve Driers
By:
Hafiz Muhammad Ayub
Chief Process Engineer
Molecular Sieve Desiccant
Zeolites - M2On.Al2O3.xSiO2.yH2O (metal alumina
silicates)
Synthetically produced and activated by
removing their water of hydration.
Retention by strong physical forces, rather than
by chemisorption.
Desorption by heat.
368 ft3 desiccant loaded in each vessel - bed
height of 15.5 ft.
Molecular Sieve Driers 1109-DA/DB
Designed to remove water and carbon dioxide from
synthesis gas.
Syn Gas from 105-F passes through the driers and after
passing through the filter 1109-LA/LB enters the H P Case of
1103-J.
Two vessel one in service and other under regeneration /
standby.
Moisture and CO2 analyzers AR-820 & AR-821
Adsorption/Regeneration Cycle:
Adsorption 24 hours
Depressuring 4 hours
Heating 4.5 hours
Cooling 4.5 hours
Pressurising 4.0 hours
Design Parameters
Feed Gas Syn, Gas (heating) Syn, Gas (cooling)
Flow rate lbmole/hr 9819.8 350 350
Pressure psia 913.7 909 909
Temperature OF 50 550 50
Composition mole %
N2 24.71
H2 74.11
CH4 0.87
Ar 0.31
Inlet H2O mole% 0.024
Inlet CO 2 ppmv 5.0
Outlet H2O ppmv 0.1
Outlet CO2 ppmv 1.0
Design Parameters
Vessel ID 5.5 ft
Bed Height 15.5 ft
Desiccant in one vessel 368 ft3
Total Desiccant in two vessels 736 ft3
Composition wt %
Sodium Oxide < 30
Silicon Oxide < 50
Aluminium Oxide < 40
Ammonia Synthesis
Benefits of S-200 over Conventional
Converter
1. High Conversion Rate results in:
Lower power consumption - Lower
recirculation gas
High ammonia conversion, high ammonia
separation lower refrigeration load
Larger heat recovery exothermic reaction
2. Low pressure drop 28 psi vs 85 psi (lesser
power consumption of recirculation
compressor)
Chemistry Involved
3H2 + N2 2NH3 + heat
Equilibrium reaction part of reactants
converted
Equilibrium concentration of ammonia
increases by high pressure and low
temperature
High reaction velocity at high temperature
Theoretical conversion vs reaction rate
At higher temperatures the equilibrium
percentage of ammonia will be too low while at
lower temperatures the reaction will be too low.
Optimum level of catalyst temperature
Chemistry Involved
Converter Design pressure is 2240 psig and
normal design operating pressure is about 1963
psig.
Temperatures in the catalyst beds are in the
range of 680 to 986OF
Promoted iron catalyst containing small
amounts of non-reducible oxides
Heat of reaction - 1350 BTU/lb
used in BFW Heating-1123-C
Catalyst
KM1R and KM1
Nominal Size of catalyst granules 1.5-3.0 mm
Radial flow type converter
Unreduced catalyst - 90% of iron oxide ( Fe 3O4), the
remainder being non-reducible oxides, mainly CaO,
K2O and Al2O3 (promoters)
Reduction of Iron oxide to free iron makes catalyst
active.
Pre-reduced catalyst produced by reduction and
subsequent stabilization by skin oxidation.
2 wt% O2 and non pyrophoric up to 212 OF
Water released when it is heated to 428 572 OF
Catalyst
Reduction of unreduced catalyst produce 280 Kg /
Ton Catalyst, Pre-reduced only 20Kg/ton
Normal catalyst life 10 15 years depends on
poisons and operational temperatures
Catalysts can be operated up to 1004 1022 OF
Oxygen compounds like CO, CO2 and H2O are
poisons. Mild poisoning is temporary and activity
can be restored.
Sulphur and Phosphorous compounds are
permanent poisons.
Process Description
Ammonia converter consists of a pressure vessel & a

basket.
S-200 basket is divided into a lower heat exchanger, two
adiabatic catalyst beds and an inter bed heat exchanger
The main gas stream is introduced into the converter
through the two main inlets (A) at the top of the
converter and passes downward through the outer
annulus between the basket & the pressure vessel.
At the bottom of the converter, the main gas stream
flows to the shell side of the lower heat exchanger and is
heated to the reaction temperature by heat exchange
with the converter effluent as it leaves the lower catalyst
bed.
At the shell side exit of the lower heat exchanger feed
gas is mixed with the cold shot stream to obtain the
correct inlet temperature to the 1st catalyst bed
Process Description (Contd)
Mixed with Quench gas passing through the tubes
of inter bed heat exchanger
Gas flows through the first bed radially
Cooled through Inter bed exchanger
Gas enters 2nd catalyst bed
The temperature inlet to the 2nd catalyst bed is
controlled by adjusting the quench gas rate.
Gas is then cooled in the LHE and then flows
through the outlet nozzle.
Start up heater for converter heating.
S-200 Converter
Oxygen Compounds
Recommendations on the allowable content of
carbon monoxide, carbon dioxide and water in the
make-up gas are:
1. 0 - 10 ppm Satisfactory
2. 10 - 20 ppm Not satisfactory, but operation could
be continued
3. > 20 ppm The catalyst life is affected, and it is
recommended that the make-up gas
be interrupted as follows:
1. 20-30 ppm Make-up gas could be introduced in the loop for
two days.
2. 30-40 ppm Make-up gas could be introduced for 24 hours.
3. > 50 ppm Only acceptable is short periods. The analyzer is
checked and if reading is correct, make-up gas is
interrupted.
Gas Composition
Hydrogen to Nitrogen ratio
A H2/N2 of close to 3:1 in the make-up gas is required in order
to keep the H2/N2 3:1 in the gas circulating in the synthesis
loop.
A small variation in this ratio of the make-up gas will have a
relatively large influence on the gas composition in the loop.
If the ratio in the loop becomes < 2.6 or > 3.2,
the reaction rate in the converter will decrease, and
the temperature will tend to decrease
while the pressure will increase at a constant make-up gas addition.
If measures are not taken to correct the ratio in the loop, the
reaction may eventually stop, and the converter will cool down
rapidly.
The recommended procedure is to increase considerable the
quantity of purge gas, which will result in a gas composition in
the loop approaching the make-up gas composition.
The make-up gas compositions should be adjusted to keep
the proper ratio when the purge gas flow is reduced to the
normal value.
Gas Composition (Contd)
Inert Level Purge Rate:
The make-up synthesis gas and the recycle gas contains,
hydrogen, nitrogen, methane and argon.
The methane and argon are inerts and tend to accumulate in
the synthesis loop.
The effective pressure for ammonia synthesis is the partial
pressure of H2 & N2 (in the optimum ratio), inerts in the
system lower this effective pressure and retard the
production.
Inerts are removed in two ways
1. Some inerts are dissolved in the product
2. but the bulk of the inerts is removed by purging some re-circulating
gas.
The inert level (or the purge gas rate) should be selected on
the basis of an optimization of the product yield versus the
power consumption of the make-up gas compressor.
A low loop pressure (i.e. a low power consumption) would
necessitate a high purge gas rate (i.e. low product yield) and
vice versa.
Gas Composition (Contd)
Ammonia Concentration at Converter Inlet:
Variation of the ammonia concentration at converter

inlet has a considerable effect on the synthesis
reaction
A decrease of the ammonia concentration at the
converter inlet will favour the synthesis reaction
It will at constant make-up gas addition allow for
operation at a lower pressure or with a lower purge
gas rate.
Recirculation Rate
The maximum amount of re-circulating gas
depends on the loop pressure and the
rotational speed of the synthesis gas
compressor. The latter is adjusted in
accordance with the load on the make-up
gas part of the compressor.
Normally, the loop should be operated at the
maximum recirculation rate.
A decrease of the recirculation rate would
cause an overall energy loss.
Loop Pressure and Purge Rate
In normal operation, the purge rate is kept at a
constant rate, whereas the pressure is self adjusting in
accordance with the load, the selected purge gas rate
and the operating conditions in the loop.
The purge gas rate should be adjusted in a manner
that the optimum inter-relationship between the power
consumption of the synthesis gas compressor and the
product yield is achieved.
Temperature Conversion Curve S-200
Three Bed Converter
Temperature Conversion Curve
Three Bed Converter

Ammonia Synthesis and Molecular Sieve

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Ammonia Synthesis and Molecular Sieve

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Ammonia Synthesis &

Molecular Sieve Driers

Bed Height 15.5 ft

Desiccant in one vessel 368 ft3

Total Desiccant in two vessels 736 ft3

Ammonia converter consists of a pressure vessel & a

Variation of the ammonia concentration at converter

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