Two main types of production process for ammonia synthesis gas are currently in

operation in Europe:-
- Steam reforming of natural gas or other light hydrocarbons (Natural Gas Liquids,
Liquefied Petroleum Gas, Naphtha)
- Partial oxidation of heavy fuel oil or vacuum residue

Anhydrous ammonia is synthesized by reacting hydrogen with nitrogen at a molar

ratio of 3 to 1, then compressing the gas and cooling it to -33C (-27F). Nitrogen is
obtained from the air, while hydrogen is obtained from either the catalytic steam
reforming of natural gas (methane [CH4]) or naphtha, or the electrolysis of brine at
chlorine plants
Six main process steps are required to produce synthetic ammonia using the
catalytic steam reforming method: (1) natural gas desulfurization, (2) catalytic
steam reforming, (3) carbon monoxide (CO) shift, (4) carbon dioxide (CO2) removal,
(5) methanation, and (6) ammonia synthesis. The first, third, fourth, and fifth steps
remove impurities such as sulfur, CO, CO2 and water (H2O) from the feedstock,
hydrogen, and synthesis gas streams. In the second step, hydrogen is manufactured
and nitrogen (air) is introduced into this 2-stage process. The sixth step produces
anhydrous ammonia from the synthetic gas. While all ammonia plants use this basic
process, details such as operating pressures, temperatures, and quantities of
feedstock vary from plant to plant.
1. Natural Gas Desulfurization
In this step, the sulfur content (as hydrogen sulfide [H2S]) in natural gas is reduced
to below 280 micrograms per cubic meter (g/m3) (122 grams per cubic feet) to
prevent poisoning of the nickel catalyst in the primary reformer. Desulfurization can
be accomplished by using either activated carbon or zinc oxide. Over 95 percent of
the ammonia plants in the U. S. use activated carbon fortified with metallic oxide
additives for feedstock desulfurization. The remaining plants use a tank filled with
zinc oxide for desulfurization. Heavy hydrocarbons can decrease the effectiveness
of an activated carbon bed. This carbon bed also has another disadvantage in that it
cannot remove carbonyl sulfide. Regeneration of carbon is accomplished by passing
superheated steam through the carbon bed. A zinc oxide bed offers several
advantages over the activated carbon bed. Steam regeneration to use as energy is
not required when using a zinc oxide bed. No air emissions are created by the zinc
oxide bed, and the higher molecular weight hydrocarbons are not removed.
Therefore, the heating value of the natural gas is not reduced.
2. Catalytic Steam Reforming
Natural gas leaving the desulfurization tank is mixed with process steam and
preheated to 540C (1004F). The mixture of steam and gas enters the primary
reformer (natural gas fired primary reformer) and oil fired primary reformer tubes,
which are filled with a nickel-based reforming catalyst. Approximately 70 percent of
the CH4 is converted to hydrogen and CO2. An additional amount of CH4 is converted
to CO. This process gas is then sent to the secondary reformer, where it is mixed
with compressed air that has been preheated to about 540C (1004F). Sufficient air
is added to produce a final synthesis gas having a hydrogen-to-nitrogen mole ratio
of 3 to 1. The gas leaving the secondary reformer is then cooled to 360C (680F) in
a waste heat boiler.
3. Carbon Monoxide Shift
After cooling, the secondary reformer effluent gas enters a high temperature CO
shift converter which is filled with chromium oxide initiator and iron oxide catalyst.
The following reaction takes place in the carbon monoxide converter:
CO + H2O CO2 + H2
The exit gas is then cooled in a heat exchanger. In some plants, the gas is passed
through a bed of zinc oxide to remove any residual sulfur contaminants that would
poison the low-temperature shift catalyst. In other plants, excess low-temperature
shift catalyst is added to ensure that the unit will operate as expected. The low-
temperature shift converter is filled with a copper oxide/zinc oxide catalyst. Final
shift gas from this converter is cooled from 210 to 110C (410 to 230F) and enters
the bottom of the carbon dioxide absorption system. Unreacted steam is condensed
and separated from the gas in a knockout drum. This condensed steam (process
condensate) contains ammonium carbonate ([(NH 4)2 CO3 H2O]) from the high-
temperature shift converter, methanol (CH3OH) from the low temperature shift
converter, and small amounts of sodium, iron, copper, zinc, aluminum and calcium.
Process condensate is sent to the stripper to remove volatile gases such as
ammonia, methanol, and carbon dioxide. Trace metals remaining in the process
condensate are removed by the ion exchange unit.
4. Carbon Dioxide Removal
In this step, CO2 in the final shift gas is removed. CO 2 removal can be done by using
2 methods: monoethanolamine (C2H4NH2OH) scrubbing and hot potassium
scrubbing. Approximately 80 percent of the ammonia plants use monoethanolamine
(MEA) to aid in removing CO2. The CO2 gas is passed upward through an adsorption
tower countercurrent to a 15 to 30 percent solution of MEA in water fortified with
effective corrosion inhibitors. After absorbing the CO 2, the amine solution is
preheated and regenerated (carbon dioxide regenerator) in a reactivating tower.
This reacting tower removes CO2 by steam stripping and then by heating. The CO 2
gas (98.5 percent CO2) is either vented to the atmosphere or used for chemical
feedstock in other parts of the plant complex. The regenerated MEA is pumped back
to the absorber tower after being cooled in a heat exchanger and solution cooler.
5. Methanation
Residual CO2 in the synthesis gas is removed by catalytic methanation which is
conducted over a nickel catalyst at temperatures of 400 to 600C (752 to 1112F)
and pressures up to 3,000 kilopascals (kPa) (435 pounds per square inch absolute
[psia]) according to the following reactions:
Exit gas from the methanator, which has a 3:1 mole ratio of hydrogen and nitrogen,
is then cooled to 38C (100F).
6. Ammonia Synthesis
In the synthesis step, the synthesis gas from the methanator is compressed at
pressures ranging from 13,800 to 34,500 kPa (2000 to 5000 psia), mixed with
recycled synthesis gas, and cooled to 0C (32F). Condensed ammonia is separated
from the unconverted synthesis gas in a liquid-vapor separator and sent to a let-
down separator. The unconverted synthesis is compressed and preheated to 180C
(356F) before entering the synthesis converter which contains iron oxide catalyst.
Ammonia from the exit gas is condensed and separated, then sent to the let-down
separator. A small portion of the overhead gas is purged to prevent the buildup of
inert gases such as argon in the circulating gas system. Ammonia in the let-down
separator is flashed to 100 kPa (14.5 psia) at -33C (-27F) to remove impurities
from the liquid. The flash vapor is condensed in the let-down chiller where
anhydrous ammonia is drawn off and stored at low temperature.
Emissions and Controls
Pollutants from the manufacture of synthetic anhydrous ammonia are emitted from
4 process steps: (1) regeneration of the desulfurization bed, (2) heating of the
catalytic steam, (3) regeneration of carbon dioxide scrubbing solution, and (4)
steam stripping of process condensate. More than 95 percent of the ammonia plants
in the U. S. use activated carbon fortified with metallic oxide additives for feedstock
desulfurization. The desulfurization bed must be regenerated about once every 30
days for an average period of 8 to 10 hours. Vented regeneration steam contains
sulfur oxides (SOx) and H2S, depending on the amount of oxygen in the steam.
Regeneration also emits hydrocarbons and CO. The reformer, heated with natural
gas or fuel oil, emits combustion products such as oxides of nitrogen, CO, CO 2, SOx,
hydrocarbons, and particulates. CO2 is removed from the synthesis gas by scrubbing
with MEA or hot potassium carbonate solution. Regeneration of this CO 2 scrubbing
solution with steam produces emission of water, NH 3, CO, CO2, and MEA. Cooling the
synthesis gas after low temperature shift conversion forms a condensate containing
NH3, CO2, CH3OH, and trace metals. Condensate steam strippers are used to remove
NH3 and methanol from the water, and steam from this is vented to the atmosphere,
emitting NH3, CO2, and CH3OH. Some processes have been modified to reduce
emissions and to improve utility of raw materials and energy. One such technique is
the injection of the overheads into the reformer stack along with the combustion
gases to eliminate emissions from the condensate steam stripper.
Control & Conservation Techniques:
The following methods and techniques can be used for controlling emissions from ammonia
production plants:
Using Natural Gas as the raw material:

The use of natural gas as the raw material (feed stock) is the best way to decrease the
waste emissions from an ammonia plant. The natural gas has high hydrogen content and
a higher heating value than most of the hydrocarbons. Processes based on heavy
hydrocarbons such as oils and coal, generate waste many time greater than natural gas
based plants.

Excess Air Reforming:

The IFA recommends the use of excess air reforming for improving the waste
conservation and control of the ammonia plants [2]. The recommendation is based upon
the fact that primary reformers have low efficiencies. By reducing the share of primary
reformer in the reforming reaction, the primary reformer size and energy demand can be
decreased. While at the same time the life and efficiency of the catalysts and the catalyst
tubes is increased. This will increase the reaction share of the secondary reformer. By
supplying the air in excess to the secondary reformer, the internal firing in the secondary
reformer is increased, which makes it possible to achieve the same degree of total
reforming as in the case of conventional steam reforming process. The reduced need of
energy to the primary reformer will decrease the use of fuel gases and the hence the
emissions of combustion flue gases.

Heat Exchange Autothermal Reforming:

The heat-exchange autothermal reforming is based upon the principle that the heat of
reaction in the secondary reformer can be used to supply the heat needed to the primary
reformer for reforming reaction. This eliminates the fired furnace and hence the reformer
flue gases, thus significantly reducing the NOx and carbon oxides emissions. Excess air is
 supplied to the reforming exchanger, to increase the internal firing, which increases the
reforming reaction. According to the IFA, these processes can reduce the NOx emissions
by 50% or more as compared to the conventional steam reforming processes [2]. Kellogg
Brown & Root (formerly M.W. Kellogg Company), introduced its new process in the 1990s,
called Kellogg Brown Root Advanced Ammonia Process plus (KAAPplus [11]), which is
based upon the same principle.

Improving CO2 Removal Processes:

Most of the CO2 removal processes used in the ammonia production use some type of
absorbent for CO2 removal. These absorbents have to be regenerated after their use.
Those absorbents should be used which are easier to regenerate and do not result in toxic
releases. During the regeneration operation proper control of the process can also reduce
the waste emissions. Reducing the use of organic absorbents such as amines can also
decrease toxic releases to the environment. Use of CO2 removal processes, which do not
use any chemicals, is another way of reducing the emissions. Processes such as
adsorption and membrane treatment can be used. However, the main problems
associated with the membrane processes are the huge pressure drops in the gases after
membrane treatment and temperature sensitivity of membranes. The cost of energy to
overcome this pressure drop has to be justified before membranes can be used in the
ammonia production processes.

Improving Purge Gas Recovery:

Improving the purge gas recovery can also control waste emissions. Ammonia is
recovered from the synthesis loop purge, while the remaining gases along with small
amounts of ammonia are sent to the primary reformer for use as fuel. If the argon
present in the purge gas can be removed (i.e. after ammonia removal), then this gas can
be recycled back to the converter. Thus increasing the ammonia production.

Better Final Purification Techniques:

The main reason for purge requirement in the synthesis loop is the build up of inerts in
the recycle stream. Accumulation of these inerts hinders the ammonia conversion in the
reactor. The two inert gases present in the feed gas to the ammonia reactor are argon
and methane. These inerts keep on accumulating in the recycle stream making it
necessary to purge in order to avoid over accumulation of these inerts. If the inert gases
can be separated from the ammonia reactor feed gas, then there would be no need for
purging. Furthermore, it will also improve the conversion reaction and also decrease the
operating cost of the synthesis loop. Rectification columns, Cryogenic purification units, or
a combination of both can be used for this purpose. These units can be used prior to the
ammonia reactor, after the methanation step.

Ammonia Synthesis:

The low conversion rate of the ammonia converters is another reason for waste
generation. Most of the conventional ammonia converters (reactors) have a 12-13%
conversion. Only recently some reactors have been developed which have conversions as
high as 17%. The main reason for this meager conversion is that the ammonia synthesis
 reaction is highly exothermic. Due to this reason, the temperature of the reaction gases
increases as ammonia is formed, increasing the rate of the reaction, but shifting the
chemical equilibrium in the opposite direction. Thus the temperature for maximum
conversion decreases with the increase in ammonia concentration. With the shift of the
reaction in the opposite direction, decomposition of ammonia starts. Also the tremendous
amount of heat evolved during the reaction increases the temperature of the catalyst bed
to its maximum potential. Further increase in the temperature can permanently damage
the catalysts. In order to avoid this situation, the ammonia converters are provided with
cooling systems, which remove the heat of reaction. Heat quenching and heat exchanger
systems are the two of the many methods used for this purpose. Ammonia synthesis can
be improved by improving the converter design. Using improved heat removal techniques
and catalyst with higher temperature resistance can improve the ammonia conversion
rate. Gases increases as ammonia is formed, increasing the rate of the reaction, but
shifting the chemical equilibrium in the opposite direction. Thus the temperature for
maximum conversion decreases with the increase in ammonia concentration. With the
shift of the reaction in the opposite direction, decomposition of ammonia starts. Also the
tremendous amount of heat evolved during the reaction increases the temperature of the
catalyst bed to its maximum potential. Further increase in the temperature can
permanently damage the catalysts. In order to avoid this situation, the ammonia
converters are provided with cooling systems, which remove the heat of reaction. Heat
quenching and heat exchanger systems are the two of the many methods used for this
purpose. Ammonia synthesis can be improved by improving the converter design. Using
improved heat removal techniques and catalyst with higher temperature resistance can
improve the ammonia conversion rate.

Short description on ammonia plant block diagram

 Unit
Blocks process/operations Description

Sulphur is reacted with hydrogen to

Hydrogenation and form hydrogen sulphide and then
Desulphurization Absorptions absorbed on packed bed absorber

Primary reformer Catalytic reforming Methane converted to CO,H2,CO2

Catalytic autothermal Residual methane conversion to CO2

Secondary reformer reaction and H2

Water-gas shift
High temperature shit reaction at high
conversion temperature CO converted to CO2

Water-gas shift
Low temperature shift reaction at low
conversion temperature Residual CO converted to CO2

Carbon dioxide
absorption Chemical Absorption CO2 absorbed by G.V solution

Carbon dioxide stripping Stripping CO2 stripped from G.V

CO2 and CO traces in process gas are

Methanator Methanation converted to methane

Centrifugal To develop operating pressure for

Synthesis gas compressor compression synthesis reactor

Ammonia synthesis Double Packed bed

reactor Reactor Ammonia formation

Chilling Heat exchanger Ammonia vapor cooling

Refrigeration and
compression Screw compression To liquefy ammonia for storage

To separate traces of nitrogen, argon,

Purge gas and recovery Absorption, separation methane and hydrogen in the process

2.2.5 Partial oxidation of heavy oils

2.2.5.1 Process description

The partial oxidation process is used for the gasification of heavy feedstocks such as
residual oils and coal. Extremely viscous hydrocarbons and plastic wastes may also be
used as fractions of the feed. The partial oxidation process offers an alternative for future
utilisation of such wastes.

An air separation unit is required for the production of oxygen for the partial oxidation
step. The nitrogen is added in the liquid nitrogen wash to remove impurities from the
synthesis gas and to get the required hydrogen/nitrogen ratio in the synthesis gas.

The partial oxidation gasification is a non-catalytic process taking place at high pressure
(>50bar) and temperatures around 1,400 C. Some steam is added for temperature
modera-tion. The simplified reaction pattern is:-

-CHn - + 0.5O2 -----> CO + n/2H2

Carbon dioxide, methane and some soot are formed in addition. The sulphur compounds
in the feed are converted to hydrogen sulphide. Mineral compounds in the feed are
transformed into specific ashes. The process gas is freed from solids by water scrubbing
after waste heat recovery and the soot is recycled to the feed. The ash compounds are
drained with the process condensate and/or together with a part of the soot. In at least
two units in Europe, the soot is separated from soot water in a mainstream filtration
stage, to avoid ash build-up in the gasification cycle downstream units. The heavy metals,
such as V, Ni and Fe are recovered. The hydrogen sulphide in the process gas is separated
in a selective absorption step and reprocessed to elementary sulphur in a Claus unit.

The shift conversion usually has two high temperature shift catalyst beds with
intermediate cooling. Steam for the shift conversion is supplied partially by a cooler-
saturator system and partially by steam injection.

CO2is removed by using an absorption agent which might be the same as that in the
sulphur removal step. Residual traces of absorption agent and CO2are then removed
from the process gas, before final purification by a liquid nitrogen wash. In this unit
practically all the impurities are removed and nitrogen is added to give the stoichiometric
hydrogen to nitrogen ratio.

The ammonia synthesis is quite similar to that used in steam reforming plants, but
simpler and more efficient, due to the high purity of synthesis gas from liquid nitrogen
wash units and the synthesis loop not requiring a purge.

2.2.5.2 Steam and power system

Auxiliary boilers are required if the compressors are steam-driven. The flue-gas from
these power plants is the main source of emissions which are mainly SO2, NOx,
and CO2. The site emissions are very low if the compressors are driven by imported
electric power.