Manufacture of Urea

Unit - IV
 Raw materials

• Basis: 1000kg prilled urea

• Item Once Through Partial recycle Total Recycle
• NH3 1150kg 880kg 600kg
• CO2 1470kg 910kg 770kg
• Power 210kWH 165kWH 145kWH
• Steam 1800kg 2000kg 2400kg
• Cooling water 120000kg 70000kg 110000kg
 Reaction

• CO2 + 2NH3 NH2COONH4 ∆H = - 37,021 Kcal

• NH2COONH4 NH2CONH2 + H2O ∆H = + 6.3 kcals

 Process Description - Urea

• Urea is always made in an ammonia plant because it

produces CO2 as by product, which can be used directly
without further treatment.
• Two reactions are involved in the manufacture of urea.
• First ammonium carbonate is formed under pressure by
highly exothermic reaction between carbon dioxide and
ammonia followed by the endothermic decomposition
reaction.
 Process Description - Urea
• While the former reaction under pressure, reaches to
almost completion and the decomposition reaction
incomplete.
• Unconverted carbon dioxide and ammonia, along with un
decomposed carbamate, must be recovered and reused.
• The synthesis is further complicated by the formation of
a dimer called biuret, NH2CONHCONH2.H2O which must
be kept low because it adversely affects the growth of
some plants.
 Process Description - Urea
• Liquid ammonia, gaseous carbon dioxide and recycle
materials charged in the heat exchanger-reactor at the
pressure of 14MPs at 170 - 1900C to form carbamate,
with most of the heat of reaction carried away as useful
process steam.
• The carbamate decomposition reaction is both slow and
endothermic.
• The mixture of unreacted reactants and carbamate flows
to the decomposer.
 Process Description - Urea
• The stoichiometric ratio of CO2/NH3 conversion to urea is
essentially about 55%, but by using an excess of CO2 (or
NH3) the equilibrium can be driven as high as 85%.
• The reactor must be heated to force the reaction to
proceed. CO2 is introduced at process pressure followed
by stripper.
• All the unreacted gases and undecomposed carbamate
to be removed from the product, the urea must be
heated at lower pressure (400kPa).
 Process Description - Urea
• The reagents are reacted and pumped back into the
system.
• Evaporation and prilling or granulating produces the final
product.
• Overall, over 99% of both CO2 and NH3 are converted to
urea, making environmental problems to minimum.
• Carbamate is highly corrosive to both ordinary and
stainless steel, but with oxygen present, 300 series
stainless steel resist it very well, so some air is
introduced along with CO2 reagent to reduce system
corrosion.
 Major Engineering Problems

Autoclave variables

• The objective of autoclave reaction is to produce the

optimum economic yield.
• The conditions which affects rate of reactions are
temperature, pressure, NH3/CO2 ratio and feed rate.
 Major Engineering Problems
Autoclave variables
The urea production rate can be varied as follows
• Increase with increasing pressure
• Increase with temperature to maximum at 175-
1800C, then falls of sharply. The operating pressure
should be above the dissociation pressure
(dissociation pressure is 180atm at 190°C) for the
carbamate.
• Use no excess ammonia.
 Major Engineering Problems
Autoclave variables
Reasons for not operating at maximum temperature
and pressure without excess ammonia
• Increased pressure increases capital and operating
cost of compression and reaction equipment.
• At higher temperature urea decomposed to biuret,
which is detrimental to germinating seeds and toxic
to animals.
• The above process conditions enhance corrosion
rates to machinery
 Major Engineering Problems

Carbamate decomposition and recycle

• It is optimized by short residence times in a stripping

column operating at low pressure and high temperature.

• Later should be below 1100C if hold up time exceeds 1-2

seconds to avoid biuret formation.

• Use of millisecond contact time in a flash evaporator

allows 1400C operating temperatures in the high recycle
design.
 Major Engineering Problems

Carbamate decomposition and recycle

• Main difference in competing processes is in the recycle
design.
• Since conversion is only 40-50% per pass, the unreacted
off gases must be recirculated or used economically
elsewhere.
• Recompression of off gases is virtually impossible
because of corrosion and formation of solid carbamate in
compressors.
• A solution is formed and pumped into the autoclave.
 Major Engineering Problems

Production of granular urea (Prilling)

• Problem again is biuret formation. Vacuum drying of 80%
urea to > 99% and spraying to air cooled and solidify
must be done just above the melting point of urea and
with a minimum residence time.
Heat dissipation in the autoclave
• The exothermic heat of reaction can be removed by
coils, wall cooling, or by adding excess reactant to
provide sensible heat pick up.
 Major Engineering Problems

Corrosion
• It can be minimized by use of the corrosion resistant
metals and maintaining the proper reaction conditions.
• High cost silver or tantalum liners are used in the
autoclaves with titanium, stainless (321SS) and
aluminum alloys used in other parts of the plant.
• Minimum temperature and pressure with excess NH3 are
desirable to reduce the severe corrosion rates.
 Properties of Urea
• Molecular formula: CH4N2O
• Molecular weight : 60.06gm/mole
• Appearance : White granules
• Odour : Odourless
• Bulk density : 673-721kg/m3
• Angle of repose : 300
• Melting point : 132-1350C
• Density : 1.32gm/ml
• Solubility : Solubility in water, ethanol, glycerol
• Moisture : 1% by wt. (Max.)
 Properties of Urea

• It is highly soluble in water and practically non-toxic

(LD50 is 15 gm/kg for rat).
• Dissolved in water, it is neither acidic nor alkaline.
• As soon as urea dissolves in the soil, it forms around it a
zoning layer of high pH and ammonia concentration
turning the soil to be acidic and toxic at the same level.
• Urea is high moisture absorbent therefore it should be
stored in sealed and well enclosed bags.
 Uses of Urea
• As a fertilizer
• As a protein food supplements for ruminant
• As an ingredient in the manufacture of resins,
plastics, adhesive, coatings
• Textiles anti-shrink agents and ion exchange resins
• In melamine production
• It is an intermediate in the manufacture of
ammonium sulfamate, sulfamic acid and
pthalocyanines.
 References

Austin, G.T.,Shreve’s Chemical Process Industries,

Fifth Edition, McGraw- Hill International Book Co,
Singapore, 1984

Dryden, C.E., Outlines of Chemicals Technology,

Edited and Revised by Gopala Rao, M. and M.Sittig,
Second Edition, Affiliated East-West press, 1993.

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