Lecture 4

Ammonia: Production and Storage - Part 1

Ammonia or azane is a compound of nitrogen and hydrogen with the formula NH3. It is a
colourless gas with a characteristic pungent smell. Ammonia contributes significantly to the
nutritional needs of terrestrial organisms by serving as a precursor to food and fertilizers.
Ammonia, either directly or indirectly, is also a building-block for the synthesis of many
fertilizers, pharmaceuticals and is used in many commercial cleaning products. Although in
wide use, ammonia is both caustic and hazardous. In 2006, worldwide production was
estimated at 146.5 million tonnes.

Ammonia, as used commercially, is often called anhydrous ammonia. This term

emphasizes the absence of water in the material. Because NH3 boils at −33.34 °C (−28.012
°F) at a pressure of 1 atmosphere, the liquid must be stored under high pressure or at low
temperature. “Household ammonia” or “ammonium hydroxide” is a solution of NH3 in
water. The concentration of such solutions is measured in units of the Baumé scale
(density), with 26 degrees baumé (about 30% w/w ammonia at 15.5 °C) being the typical
high-concentration commercial product. Household ammonia ranges in concentration from
5 to 10 weight percent ammonia.

Approximately 83% (as of 2004) of ammonia is used as fertilizers either as its salts or as
solutions. When applied to soil, it helps provide increased yields of crops such as corn and
wheat. Consuming more than 1% of all man-made power, the production of ammonia is a
significant component of the world energy budget.

4.1 Physical properties of ammonia

Ammonia has flammable limits of 16%-25% by volume in the air and 15%-79% in oxygen.
Ammonia –air mixtures is 650 Celsius. The mixture can explode if ignited. Ammonia is
readily soluble in water. A large amount of heat, about 2180kj (520kcal), is produced when
the dissolution of 1kg of ammonia gas occurs.
4.2 Physical properties of anhydrous Ammonia

Property Unit Value

Molecular weight 1 17.03

o
Boiling point C -33.35
o
Freezing point C -77.7
o
Critical temperature C 133.0

Critical pressure MPa 11.425

Specific heat (gas) j/kg oK

-at0oC 2,097.2

-at100 oC 2,226.2

-at200 oC ` 2,105.6

Heat of formation (gas) kj/mol

-at 0 oK -39.2

-at 298 oK -46.2

Solubility in water %, weight

-at 0 oC 42.8

-at 20 oC 33.1

-at 40 oC 23.4

-at 60 oC 4.1

Specific gravity g/ml

-at -40 oC 0.690

-at 0 oC 0.639

-at 40 oC 0.580
4.3 Density of Ammonia at 150C

Ammonia (wt %) Density (g/cm3)

8 0.970

16 0.947

32 0.889

50 0.832

75 0.733

100 0.618

4.4 Production of Ammonia

Ammonia is produced in a process known as the Haber process, in which nitrogen and
hydrogen react in the presence of an iron catalyst to form ammonia. The hydrogen is
formed by reacting natural gas and steam at high temperatures and the nitrogen is supplied
from the air. Other gases (such as water and carbon dioxide) are removed from the gas
stream and the nitrogen and hydrogen passed over an iron catalyst at high temperature and
pressure to
form the ammonia. The process is shown schematically in Figure 4.1.
 Primary Secondary
 
Hydrodesulphuriser Reformer Reformer High Low
Air Temperature Temperature
  Steam Shift Shift

400°C Steam 550°C

  Cooling
350°C 200°C
H2 Steam
 
Natural Super heater
Gas
 
220°C
1000°C 420°C
Steam Steam
  790°C
390°C raising raising Heat
Recovery
  Preheater
400°C Process
CO2 290°C Condensate
 
Cooling Quench
400°C
  Reboiler
Quench

  Cooling Refrigeration
220Bar
Steam
  330°C
470°C
Heat Cooling Boiler
Recovery Liquid Ammonia
  Cooling Purge Gas
Condensate
Carbon Dioxide
 
CO2 Removal Methactor Ammonia Synthesis

Fig. 4.1 Industrial manufacturing of Ammonia

Step 1 - Hydrogen production

Hydrogen is produced by the reaction of methane with water. However, before this can be
carried out, all sulfurous compounds must be removed from the natural gas to prevent
catalyst poisoning. These are removed by heating the gas to 400oC and reacting it with zinc
oxide:
ZnO + H2S → ZnS + H2O
Following this, the gas is sent to the primary reformer for steam reforming, where
superheated steam is fed into the reformer with the methane. The gas mixture heated with
natural gas and purge gas to 770oC in the presence of a nickel catalyst. At this temperature
the following equilibrium reactions are driven to the right, converting the methane to
hydrogen, carbon dioxide and small quantities of carbon monoxide:
CH4 + H2O →3H2 + CO
CH4 + 2H2O → 4H2 + CO2
CO + H2O → H2 + CO2
This gaseous mixture is known as synthesis gas.

Step 2 - Nitrogen addition

The synthesis gas is cooled slightly to 735oC. It then flows to the secondary reformer
whereit is mixed with a calculated amount of air. The highly exothermic reaction between
oxygen
and methane produces more hydrogen. Important reactions are:
CO + H2O → CO2 + H2
O2 + 2CH4 → 2CO + 4H2
O2 + CH4 → CO2 + 2H2

2O2 + CH4 → 2H2O + CO2

In addition, the necessary nitrogen is added in the secondary reformer. As the catalyst that
is used to form the ammonia is pure iron, water, carbon dioxide and carbon monoxide must
be removed from the gas stream to prevent oxidation of the iron. This is carried out in the
next three steps.