ADIGRAT UNIVERSITY COLLEGE OF ENGINEERING AND

TECHNOLOGY
DEPARTMENT OFCHEMICAL ENGINEERING
PROCESS INDUSTRIES I

Chapter two
Nitrogen industries
The Process Technology of Ammonia production

By : Mengsteab N.

1
 Introduction

• Ammonia (NH3):-It is the most important

nitrogenous material.
• It is a colorless alkaline gas, is lighter than air and
possesses a unique ,penetrating odor.
• Ammonia gas was first produced as pure
compound by priestly in 1774.
• It is the base from which virtually all nitrogen-
containing products are derived.
• Major raw material for industry and agriculture.

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 Cont..

• 80% of ammonia production is used in

fertilizer, 15% of ammonia is used in plastics
and fibers and 5% in commercial and military
explosives.
• ammonia is the primary nitrogen source used
in fertilizer
• Commercial grades includes pure liquid
ammonia and aqueous ammonia usually
standardized at 28% ammonia.

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 Physical properties

• The flammable limit of ammonia in air are 16-25

%;in oxygen the range is 15-79%.such mixture can
explode although ammonia-air mixture are quite
difficult to ignite. The ignition temperature is
about 6500C.
• Ammonia is an excellent solvent for slats, and has
exceptional capacity to ionize electrolytes.
• The alkaline metals and alkaline earth
metal(except beryllium) are readily soluble in
ammonia. Iodine , sulphur and phosphorus
dissolve in ammonia.

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 Chemical Properties

• Ammonia is comparatively stable at ordinary temperatures,

but decompose into nitrogen and hydrogen at elevated
temperatures
• at atmospheric pressure, decompositions begins at about
450-500 0C ,whereas in the presence of catalysts, it begins
at low at 3000C and is nearly complete at 500 -6000C.At
10000C,however ,a trace of ammonia remains.
• Ammonia reacts readily with a large variety of substance.
Oxidation at a high temperature is one of the more
important reaction, giving nitrogen and water. Gaseous
ammonia is oxidized to water and nitrogen when heated to
relatively high temperate are on the presence of metals,
such as cupric oxide

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 Uses of Ammonia
1)The petroleum industry utilizes ammonia in neutralizing the
acid constituents of crude oil and for protection of equipment
from corrosion. Ammonia is used in the mining industry for
extraction of metals such as copper, nickel and molybdenum
from their ores.
2)Ammonia is used in several areas of water and wastewater
treatment, such as pH control, in solution form to regenerate
weak anion exchange resins, in conjunction with chlorine to
produce potable water and as an oxygen scavenger in boiler
water treatment.
3)Ammonia is used in stack emission control systems to
neutralize sulfur oxides from combustion of sulfur-containing
fuels, as a method of NOx control in both catalytic and non-
catalytic applications and to enhance the efficiency of
electrostatic precipitators for particulate control.

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 Cont..
4)Ammonia is used as the developing agent in
photochemical processes such as white printing and blue
printing
5)Ammonia is a widely used refrigerant in industrial
refrigeration systems found in the food, beverage, petro-
chemical and cold storage industries.
6)Ammonia is used in the rubber industry for the
stabilization of natural and synthetic latex to prevent
premature coagulation.
7)The food and beverage industry uses ammonia as a
source of nitrogen needed for yeast and microorganisms
8)The decomposition of ammonia serves as a source of
hydrogen for some fuel cell and other applications.

7
 Cont..
9)Ammonia is used by the leather industry as a curing
agent, as a slime and mold preventative in tanning liquors
and as a protective agent for leathers and furs in storage.
10)Weak ammonia solutions are also widely used as
commercial and household cleaners and detergents.
11)Agricultural and fertilizer industry
• Production of (NH4)3PO4 , NH4NO3 , (NH4)2SO4
12)Nitric Acid Production
13)Pulp and paper industry –for pulping wood
14)Textile industry –manufacture of synthetic fibers such
as nylon and rayon.

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 The process technology of ammonia
production
Inputs and Raw materials sources for ammonia
production includes:
1.Hydrogen containing materials (hydrogen source)
2.Water( for steam generation)
3. Air(Nitrogen source)
• The primary raw material or resources of
hydrogen and energy are hydrogen containing
materials such as Natural Gas (NG) or petroleum
or coal, water and biomass.
• Air provides Nitrogen and Oxygen

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 Raw material source selection
The following hydrocarbons are source of
hydrogen for ammonia production.
1) Natural gas
2) Heavy oil
3) Coal
The following table is an approximate
comparison of the energy consumption, the
investment cost and production cost for the
three feed stocks.
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Cont…

11
 Cont…
Natural gas is therefore the most appropriate
source of feedstock on all the three accounts.
Natural gas will dominate as feedstock for ammonia
production in the foreseeable future.
Coal may become a competing feedstock if the
prices of natural gas and petroleum products go
very high due to depleting resources.
For the present time and near future, the steam/air
reforming process based on natural gas is
considered to be the most dominating and best
available technique for production of ammonia.
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 Cont…
Ammonia production Technology is almost
Hydrogen production Technology.
Hydrogen production Technology:
1)Steam reforming
2)Partial oxidation
3)Water Electrolysis

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 MAJOR UNIT OPERATIONS OF NATURAL GAS BASE
AMMONIA SYNTHESIS TECNOLOGY

1.DESULPHURISATION
2.PRIMARY REFORMER
3.SECONDARY REFORMER
4.WASTE HEAT BOILER (WHS)/Heat recovery
5.HT SHIFT &LT SHIFT
6.CO2 REMOVAL (WASH)
7.METHANATION
8.COMPRESSOR
9.AMMONIASYNTHESIS

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 Cont…
1. Feedstock desulphurization
• Natural gas typically contains significant levels of sulphur and
sulphur compounds,5-30 mg S/Nm3feed gas.
• Sulphur must be removed as it can poison the reforming catalysts in
downstream
• Sulphur compounds need to be reduced to a concentration of less
than 2 mg S/Nm3 feed gas.
• To remove the sulphur, the natural gas is heated to a temperature
of 300 ° C to 400 ° C in the presence of hydrogen (usually recycled
from the synthesis section), thereby hydrogenating the sulphur
compounds to H2S, which is then adsorbed onto pelletized oxide
for later disposal:
R-SH + H2 ⇔ H2S + R-H, (R = alkyl group)
H2S + ZnO ⇔ ZnS + H2O

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Cont…

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 Cont…
2.Primary/Steam Reforming
• Gas from the desulphuriser is compressed, mixed with excess steam and
the preheated mixture enters the primary reformer at a temperature in
the range of 400 – 600 °C.
• The heated desulphurized natural gas and the steam then reacted in the
presence of a nickel or nickel-chromium catalyst.
• The composition of the outlet stream depends primarily upon the
following equilibria:
• CH4 + H2O ⇔ CO + 3H2 206 kJ/mol
• CO +H2O ⇔ CO2 + H2
• The first reaction is highly endothermic, and heat is supplied mainly by
firing natural gas.
• 50% to 60% of the total generated heat is used in the reaction; the heat
released as flue gas to produce steam for use .

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Cont…

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 Cont…

• The primary reformer consists of a large number of

catalyst filled tubes.
• The applied steam to carbon molar ratio (S/C ratio) is
typically around 3.0; although the actual optimum ratio
depends on several factors, such as the feedstock
quality, purge gas recovery, primary reformer capacity,
shift operation, and the plant steam balance. In new
plants, the optimum S/C ratio may be lower than 3.0.
• Upon leaving the primary reformer, the gas is a mixture
of CO2, CO, H2O, CH4 and H2 at a temperature of
approximately 800 ° C to 900 ° C.

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 Cont…
3. Secondary Reformation
• In the primary reformer, only 30-40% of the hydrocarbon feed is reformed to
Hydrogen
• The main objective of secondary reforming is to add the nitrogen required for the
synthesis and to complete the conversion of the hydrocarbon feed.
• This is done in secondary reformer where process gas is mixed with preheated
compressed air and then passed over nickel catalyst. The reformer outlet
temperature is about 1000°C, and up to 99 per cent of the hydrocarbon feed to
primary reformer is converted.
• The further combustion of the un-reacted methane hydrocarbons raises the
temperature to over 1000 ° C, allowing the remaining methane to be converted to
H2 and CO. The temperature must be increased to increase the conversion, the
result that the methane is converted down to a residual content of around 0.2 –
0.3 %.
• The outlet gas from the secondary reformer consists primarily of CO2, CO,H2, and
N2 and it is cooled immediately to 350 ° C and 450 ° C downstream of the reformer

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Cont…

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 Cont…
Waste Heat Boiler
The outlet gas from the secondary reformer
consists primarily of CO2, CO,H2, and N2 and it
is cooled immediately to 350 ° C and 450 ° C in
Waste Heat Boiler installed after secondary
reformer

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 Cont…
4.Shift conversion :The process gas from the secondary reformer
contains 12 – 15 % CO (dry gas base). Most of this CO will be converted
in the shift section to CO2 and H2., according to the reaction:
CO + H2O CO2 + H2 (- 41 kJ/mol)
• This reaction is carried out in two steps with intermediate heat
removal, a) a high temperature shift (HTS) and b) a low temperature
shift (LTS).
• In the HTS, process gas mixes with high-pressure steam and passes
over a FeO/Cr catalyst at a temperature of about 400 ° C. The
process gas is then cooled to around 200 ° C the HTS , where
remaining CO is shifted to CO2 over a CuO/ZnO catalyst.
• The process gas is then condensed to remove excess steam
(condensate) before removal of CO2.

23
 Cont…

• a high temperature (HTS) favours reaction velocity, while low

temperature (LTS) favours product formations, so for this two shift
conversion steps are applied in series.
• Initially, the process gas is passed through a bed of iron
oxide/chromium oxide catalyst at 350 – 380 °C and then over a
copper oxide/zinc oxide catalyst at approximately 200 – 220 °C. The
final residual CO content of the gas is 0.2 – 0.4 %.
• New developments can enable an isothermal shift one-step
conversion to take place, applying an internal cooling of the process
gas with cooling tubes running through the catalyst layers.
• The shift process reduces CO to ppm which prevents poisoning of
the catalysts during the ammonia synthesis step. CO2 is much
easier to remove than CO.

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 Cont…
5. Carbon Dioxide Removal
• After shift conversion , the process gas contains mostly H2, N2, CO2.
• The CO2 (formerly CO) is also detrimental to the synthesis catalysts, so it
too must be removed.
• CO2 removal is by both chemical and physical processes, where the CO2
either reacts with or is adsorbed onto a circulating chemical solvent
solution.
• This CO2/solvent solution is then regenerated via a stripper, from which
the CO2 may be either vented to waste or collected for use elsewhere.
• The solvents used in chemical absorption processes are mainly aqueous
amine solutions, e.g. mono ethanolamine (MEA) activated methyl
diethanolamine (aMDEA) or hot potassium carbonate solutions. Other
typicalchemical solvents are glycol dimethylethers (Selexol), potassium
carbonate and others. The regeneration of the solvents (in the stripper)
occurs by steam stripping or by flash tanks

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 Cont…

• This process step removes the CO2 from the reaction gas and the
quantity corresponds to nearly all the carbon introduced as feed gas
into the overall process.
• The residual CO2 content is usually in the range of 50 – 3000 ppm.
The CO2 is removed in a chemical or physical absorption process.
• Another emerging process is pressure swing adsorption (PSA). This
process has the potential to combine in one step both the classical
CO2 removal and the methanation (next process step).This is valid
for all cases where the CO2 purity is unimportant. However, if pure
CO2 is needed as a product, then a classical solvent scrubbing of
the low pressure off-gas of the PSA can be used to recover CO2.

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Cont…

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 cont…
6. Methanation
• Any small amounts of CO and CO2 still remaining in the synthesis
gas are converted to inert methane by catalytic methanation (which
is the reverse of the reforming reactions/ hydrogenation).
• The small amounts of CO and CO2, remaining in the synthesis gas,
can poison the ammonia synthesis catalyst and must be removed
usually by conversion to CH4 by hydrogenation in the methanator:
CO + 3H2 ⇔ CH4 + H2O H = -206 kJ/mol
CO2 + 4H2 ⇔ CH4 +2H2O H = -165 kJ/mol
• These reactions take place at a temperature of around 300 °C in a
reactor filled with a nickel based catalyst. The residual
concentration of these carbon oxides is usually less than 10 ppm.
• Methane is not involved in the synthesis reaction, but the water
formed must be removed by drying before entering the converter.

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 Cont…
7.Compression
Modern ammonia plants use centrifugal compressors to
pressurize the synthesis gas to the required level (100 –
250 bar, 350 – 550 °C) for ammonia synthesis. Molecular
sieves are sometimes used after the first compressor
stage to remove the last traces of H2O, CO and CO2 from
the synthesis gas. These compressors are usually driven
by steam turbines, utilizing steam produced from the
excess process heat. A small quantity of condensates is
removed from the synthesis gas during compression.
These condensates still contain ammonia.

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 Cont…
8. Ammonia Synthesis
Purified synthesis gases are cooled and compressed, then they are passed
over an iron catalyst in the ammonia converter. Synthesis typically occurs at
20 MPa to 30 MP at a temperature of 350oC to 550oC, but it is reversible,
such that the amount of ammonia formed depends strongly upon
temperature and pressure in the reaction vessel – a matter of primary
importance to the plant operator:
N2 + 3H2 ⇔ 2NH3 H = -46 kJ/mol (Haber process)
Even at optimum temperature and pressure, only 20-30% of the synthesis gas
reacts per pass.
• Formed NH3 is removed by refrigeration, and unreacted gases are
recycled back to the converter.
• In order to produce sufficiently low temperatures to favour ammonia
condensation, pressurized ammonia is itself used as a refrigerant.
• Product ammonia is sent to atmospheric storage tanks equipped with
refrigeration.

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 Effect of pressure and temperature on
ammonia production
• Le Chatelier’s Principle states that whatever is done to a reaction, the reaction will
act to oppose it. Example: If a product in an reversible reaction is removed,more
product will be produced to re-establish the equilibrium It may be applied to
pressure, temperature and concentrations of reactants and products.
• Increasing the pressure causes the equilibrium position to move to the right
resulting in a higher yield of ammonia since there are more gas molecules on the
left hand side of the equation (4 in total) than there are on the right hand side of
the equation (2). Increasing the pressure means the system adjusts to reduce the
effect of the change, that is, to reduce the pressure by having fewer gas molecules.
• Decreasing the temperature causes the equilibrium position to move to the right
resulting in a higher yield of ammonia since the reaction is exothermic (releases
heat). Reducing the temperature means the system will adjust to minimise the
effect of the change, that is, it will produce more heat since energy is a product of
the reaction, and will therefore produce more ammonia gas as well However, the
rate of the reaction at lower temperatures is extremely slow, so a higher
temperature must be used to speed up the reaction which results in a lower yield
of ammonia.

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Block diagram of ammonia synthesis

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Process flow diagram of ammonia
synthesis

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