Ammonia

Manufacturing
 Introduction

Ammonia is compound of nitrogen and hydrogen with formula NH3. At

standard temperature and pressure ammonia is a gas. It is toxic and corrosive
to some materials and has a characteristic pungent odor. Ammonia used
commercially can be anhydrous ammonia or an aqueous solution of ammonia
and water referred to as ammonium hydroxide. Anhydrous ammonia must be
stored under pressure or at low temperature to remain a liquid.
 Uses of Ammonia
➢In addition to serve as a fertilizer ingredient in urea and ammonium nitrate, it can
also be used directly as a fertilizer by forming a solution with irrigation water,
without the addition of any other chemical.
➢The second important use of ammonia is in the production of nitric acid.
➢Ammonia has good thermodynamics properties that make it a very suitable
refrigerant. Since it liquefies readily under pressure and was used in virtually all
refrigeration units prior to the advent of haloalkane.
➢It also some times added to drinking water along with chlorine to form
chloramines a disinfectant.
➢It is used to manufacture a lot of other chemicals compounds like HCN and
explosives etc.
Block Diagram Of Steam Reforming Process
 Feedstock Desulfurization

Most of the catalysts used in the process are sensitive to sulfur and sulfur
compounds. The feedstock normally contains upto 5 mg/Nm3(normal m3) as
sulfur compounds. The feedstock is pre heated to 350-400 °C and then treated in a
desulfurization vessel, where the sulfur compounds are hydrogenated to H2S,
typically using a Cobalt molybdenum catalyst and then adsorbed on pelletized
ZnO.
R-SH + H2 H2S + RH
H2S + ZnO ZnS + H2O
In this way sulfur is remove to less than 0.1ppm sulfur in the gas feed. The ZnS
remains in the adsorption bed. The hydrogen for the reaction is usually recycled
from the synthesis reaction.
 Steam Reforming
Primary Reforming
The gas from desulfurizer is mixed with process steam. Mixture is then heated
further to 500-600 °C before entering the primary reformer. The primary reformer
consist of a large number of high nickel chromium alloy tubes filled with nickel
containing reforming catalyst. The overall reaction is highly exothermic. The
composition of the gas leaving the primary reformer is given by the close
approach to the following chemical equilibria.

CH4 + H2O CO + 3H2 ΔH=206kJ/mol

CO + H2O CO2 + H2 ΔH= - 41kJ/mol
The heat for the primary reforming process is supplied by natural gas or other fuel.
Secondary Reforming

Upto 85% hydrocarbon feed is reformed in the primary reformer because

of the chemical equilibria at the actual operating conditions. The
temperature must be raised to increase the conversion. This is done in the
secondary reformer by internal combustion of the part of gas with process
air, which also provides the N2 for the final synthesis gas.
H2 + Air N2 + H2O
The process gas is cooled 350-400 °C in a waste heat boiler.
 Shift Conversion
Process gas form the secondary reformer contains 12-15% CO (dry gas bases)
and most of the CO is converted in the shift section to CO2 according to the
reaction.
CO + H2O CO2 + H2 ΔH= - 41kJ/mol
In the high temperature shift conversion (HTS), the gas is passed through a bed
of iron oxide/ chromium oxide catalyst at around 400 °C, where the CO content
are reduced to 3%(dry gas base), limited by shift equilibrium at the actual
operating temperature. The gas from HTS is further cooled to increase the
conversion through the low temperature shift (LTS) converter. The LTS converter
is filled with a zinc oxide based catalyst and operated at about 200 – 220 °C. The
residual CO content in converted gas is 0.2 - 0.4%(dry gas base).
 CO2 Removal
• The process gas from LTS converter contains mainly H2, N2, CO2 and the excess
process steam. The gas is cooled and most of the excess steam is condensed
before it enters the CO2 removal System.
• The CO2 is removed in a chemical or physical absorption process.
• The solvent used in chemical absorption processes are mainly aqueous amnie
solution ( Mono Ethanolamine (MEA) ), Activated Methyl Di-Ethanolamine
(AMDEA) or hot potassium carbonate solutions.
• Physical solvents are glycol, di-methyl ethers (selexol), Propylene carbonate and
other.
 Methanation

The small amount of CO and CO2 , remaining in the synthesis gas, are poisonous
for the ammonia synthesis catalyst and must be removed by conversion of CH4 in
the methanation
CO + 3H2 CH4 + H2O
CO2 + 4H2 CH4 + 2H2O
The reaction take place at around 300 °C in the reactor filled with a nickel
containing catalyst. Methane is an inert gas in the synthesis reaction but the water
must be removed before entering the convertor. This is done by cooling and
condensing the downstream of the methanator.
 Synthesis Gas Compression
After methanation, the gas pressure is 27 kg/cm2 and temperature is 364 °C.
This gas is pressurized to 151 Kg/cm2 as required by the synthesis reaction.
Modern Ammonia plants use centrifugal compressor for synthesis gas
compression, usually driven by stream turbines with the steam being produced
in the ammonia plant.
 Ammonia Synthesis
The synthesis of ammonia takes place on an iron catalyst at pressure usually in
the range 100-250 bar and temperature 350-550 °C.

N2 + 3H2 2NH3 ΔH = - 46 kJ/mol

Only 20-30% is reacted per pass in the reactor due to the unfavorable equilibrium
conditions. The ammonia that is formed is separated from the recycle gas by
cooling/condensation, and un-reacted is substituted by the fresh make up
synthesis gas, thus maintaing the pressure. In addition, extensive heat exchange is
required due to exothermic reaction.
 NH3 Purification
• Conventional reforming with methanation as the final purification step
produces a synthesis gas containing inerts ( methane and argon) in quantities
that do not dissolve in the condensed Ammonia.
• The major part of these inert are removed by taking out a purge stream from the
loop. The purge gas is scrubbed with water to remove ammonia before being
used as fuel or before being sent for hydrogen recovery.
 Energy Conservation
Conservation and reuse of heat is so vital that it has been said that an ammonia
plant is really a steam generating plant that incidentally produces much more
steam than ammonia (4:1).