UREA

Uea xcupies the third place among the world's solid nitrogenous fertilizers, but it is the highest in
nutrient ooncentration because, if pure, it contains nearly 45.47% nitrogen. The most important properties
t tertulizer grade urea are given in the following table.
Urea came into
prominene
as a fertilirer
1950. There are
in
Table (3) Properties of fertilizer grade urea
some practical difficulties en- Nitrogen percentage 45%
countered with urea. The
biuret|2. Solubility, g/100 mL. H,0 at 25 °CC 19
(NH.CONHCONH;) content is3.
Melting point |132.7°C
regarded as an
important prop- 4. Particle size
erty of urea, because under cer- 95%-8 mesh, + 16 mesh
tain conditions a small Hygroscopic point, % 72
percentage can cause plant tox-
6. Sp.gravity 20/4'C 1.335
icity. This is true when urea is
||7. Bulk density, lb/ft" 42 45
used in citrous crops.
Another property adverse to urea is its tendency to
hydrolyse and lose ammonia, a reaction promoted
by high temperature, low pH and certain catalysts. In some respects, it is desirable, because it must
occur
before plants can use the nitrogen
efficiency, but if the urea is applied to the surface of the soil, ammonia
produced by hydrolysis can be lost to the atmosphere befere it has time to combine with soil
High tenmperature aggravates hydrolysis. Another adverse property of urea is its slower constituents.
nitrate in the soil (called nitrificaion) as conversion to
compared with ammonia, ammonium nitrate or ammonium
sulphate. The urea must hydrolyse and release ammonia, whereas the other materials are
ammonical form or in the case of ammonium nitrate, already in the
already partially in the nitrate form. In very cold
places, urea may not produce nitrate nitrogen as rapidly as desired.
RAW MATERIALS
Like ammonium nitrate, urea is always made in an ammonia
ammonia producion is that most ammonia plant. The reason for associating urea
plants produce carbon dioxide as a byproduct which can be
 ol a major raw malcral at
manufacture without further treatment. This availability
usea
directly for urea
I Cost 1S one of the main reasons for the relatively low cost of prOducing urca.
The used lor producing
CO2 available from a modern ammonia plant comes from synthesis gas
O wilh waler, lo produce
IOst of the CO in the synthesis is converted intoCO, by reaction
6 gas
the synthesis of
the principal raw material
in
as possible. Thus the initial carhbon.
nydrogen and CO2. Production of
ammonia, is converted by steps to the lower energy levels represented by C
urea realises most of the remaining chemical potential of the carbon by using the relativecly wcak
Cn
reactivity of CO to form urea.
Ammonia plants that use a source of hydrogen other than synthesis gas, such as byproduct refinery
s or
coke have the disadvantage of not being able to produce urca. The main allernative
oven gas,
source Co, is lue gas. In some places, blast furnance gas from a steel plant has becn usca to supply
of
carbon dioxide for urea
production.
MANUFACTURE
Urea can be manufactured by passing liquid CO and liquid NH in a silver lined special autoclave
when ammonium carbamate is formed. The latter is heated at 130-135" under about 35 atmospherie pressure
The conversion is about 40%. Urea remains in the
tOgeturea. aqueous solution. The resultant charge is
passed
into another vessel and steam is introduced.

2NH3+ CO2» NH,COONHa

NH,COONH4> NH,CONH2 + HO;AH = +6.3 k. cals.
Amm. carbamate Urea
Since the rate
determining step is endothermic, the overall reaction should be favoured by a rise in
temperature. But conversion of NH2COONH4 to NHCONH2 actually records
170°C and above it, it fails.
increasing yield upto about
Temperature above 200°C in a 180-200 atm. unit is not conductive, because
it promotes corrosion, and favours biuret
formation (a side reaction) at the cost of urea.
2NH,CONH2 > NH2 - CO - NH CONH2+ NH
Urea Biuret
Because the vapour pressure of ammonium carbamate is
high, its dehydration is attended with a
decrease in the number of moles. Hence increase of
pressure favours the yield of urea. The operating
pressure should be above the dissociation pressure of the carbamate at a
given temperature.
An of NH shifts the
excess
equilibrium towards the formation of urea, by combining with water
formed. Thus using slightly higher ratio of NH3: CO2 isbeneficial.
CONDITIONS FORA GOOD YIELD
(a) Carbon dioxidebe free from oxygen andhydrogen to avoid hazard of corrosion or explosion. (b)
NH-CO; ratio varies widely, ranging from about 10% excess NH over the stoichiometric amount to
100% or more. The larger excess
gives better results. (c) Preheating of ammonia is essential for better
results. (d) Reaction temperature should be as high as possible, but must be limited because of corrosion.
The maximum temperature that can be attained in stainless steel lined reactors (used in the majority of
F.
plants) is about 380 The
(e) average pressure is about 27o0 psig, but pressure as low as 2400 and as

high as 6000 psig have been reported.

 ZCT.

(a) Urea or carbamide is

IMPORTANT POINTS
high quality and most valuable
a
fertilizers with
easily assimilated by plants and can also be used nitrogen like
content. lt is a 46% nitrogen
stock feeds or animal food. directly a
nitrogen addition in live

(b) Carbamide is used

not in
in turn are agriculture, but also in industry. It is used in making
used to produce valuable urea resins which
plastics, wood-particle boards, synthetic glues, compositions
impregnating cloth ete. Urea is also used for

Urea is synthesiscd from

widely in preparing the synthetic fibres.
NH and CO2 in two stages.
(a) First of them is the formation of
ammonium carbamate
2NH+ CO » NHCOONH4+ 159.1 kJ . (1)
(b) The second stage is
dehydration of the carbamate to form a melt of urea.
NHCOONH, > (NH,)CO+ H,0 285 kJ (2)
The overall production of is
gas liquid heterogeneous process occurring in
urea a
region. In general, the manufacture involves the kinetically controlled
following stages : chemical reaction between NH3 and
CO, (synthesis), distillation of the synthesis products, and processing the urea solutions obtained in the
distillation operation into the end product. The rate of the overall
reaction is determined by
of ammonium carbamate in the melt, the slowest dehydration
stage.
(c) The equilibrium
ratios and rate of urea synthesis depend on the
temperature, pressure and chemical
composition of the system. Since the vapour pressure of ammonium carbamate is very high, and the overall
result of the synthesis reaction is a decrease in the gas volume, the
equilibrium yield of urea increases as
the pressure is increased. The rate of reaction and actual urea
yield also grow rapidly with the pressure
because of increased driving forces of the process, that is, concentration of the gas-phase reactants. The
raie of the process and particularly that of reaction (2) increases sharply with the temperature as a result
of which actual urea yicld increases. If the residence time of the rcaction mixture in the heated zone is
increased further (above 180'C) the yicld of urea decreases as a result of the speed up of side reactions.
The product yield can also be increased by using an excess of ammonia in the inilial mixture over the
stoichiometric ratio. An excess of NH, impedes formation of side products of carbamate hydrolysis and
shifts the cquilibrium of reaction (2) towards the formation of urea, because excess combines with water
formed by dehydration of the anmmonium carbamate. The excess of NH, in the reaction mixture also

decreases the apparaius corrosion.

(e) The formation of ammonium carbamate in optimum conditions proceeds almost to the end andat
a high rate. but carbamate dehydrates slowly, not completely, and is accelerated only in the liquid phase.
The duration of carbamate dehydration sharply decreases with increase in temperature and yield of urea
increasesIn addition to raising the temperature. the yield of urea can be incrcased by using pressure and
an excess of NH; above the stoichiometric amount, (as seen above) which prevents by- product formation
industry. urea synthesis is carried out without using a catalyst, at 180-200 atm and 180-200'C
emperatures. Higher temperatures can not be employed because they increase corrosion of the apparatus.
100% excess NH is used.
(g) Th: raw materials are the expansion gas obtained in the process of manufacturing NH, (contains
upto 90 CO;) and liquid NH, used in 100-125% excess over the stoichiometric amount. When using
100% CO; and absolutely pure ammonia, the urea yicld (relative to CO,) under optimum conditions is
60-70% and the molten mass obtained by dehydration of carbamate contains about 35% urea. Good
economics of the process and low cost of urea can only be achieved by using the parts of the reactants,
NH and CO2 which donot take part in the reaction. Thus unreacted NH; and CO2 are generally used
either for manufacturing other products (open systems) or are recycled to the process (closed system).

To vacuum
(NH3+CO2 + H20)
Evaporator
Air
Prilling
Molten mass tower
Liquid
ammonia

Synthesis Steam
tower Distillation
tower
Pump

Compressor Steam Condensate

Air
CO2 Condensate Condensate Tank for the -Conveyor
molten mass Urea'

Fig. 2. Flow diagram of urea production process.

(h) Figure 2 shows an open system for producing urea. Synthesis takes place in a tower made of
alloy steel. The inner cylinder of the tower acts to protect the walls of the high pressure vessel against
corosion by the reaction mixture. Liquid NH3 is fed to the annular space between the tower wall and the
inner cylinder by a pump. Il flows along the walls, protecting them from corrosion. NH; reacts with
 which is fed to the inside of the cylinder at e botion of the wwec, which operalus in plug lluw.
ne molien urea is removed from the upper part of the tower, hrotuled o almosplheric pressure and
ransferred the distillation tower, where the products of a decomposuio
to
excess NH, and Or
amuo
Ccaramate salts are stripped from the urea solution. The solution is concentrated in an evaporator andurea
stheproduced either in the form of
distillation tower are crysals or it is
granulated in a prilling tower. The gases discharged from
regenerated.
The various methods used for the
manufacture of urea differ in the methods uscd to separate and
regenerate these gases. They may be utilized in the neighbouring unit for the manufacture of NH,NO, or
may be separaled by selective absorption of CO, or of NH, with one of a number of sorbents. both

reagents being relurned to the process (gas-phase recycle), or may be uilized io torm a
suspeusion ot
anmonium carbamate in the oil (by
which is recycled to the
absorbing
both and Co, from the gas with an incrt mineral
NÅ, oil)
synthesis tower or by returning NH, and CO to the processing cycle in the torm
of aqueous solutions of ammonium salts
(liquid-phase recycle) etc.
 ACTION OF UREA AS FERTILIZER
Urea is first hydrolysed by soil water to NH, and CO. Then nitrosification of NH; takes place by
the ageney of nitrosomonas and nitrosococcus bacteria and nitrites are formed. Nitrification of nitriles IS
brought about by nitrobactor bacteria to fom nitrates utilized by the plants in the soil.
co(NH)+ H,O -»Co, + 2NH,
Baccna
2NH+ 30 2NO.2H,O+ 2H+ Energy
Bacteria
2NO+O, 2NO+ Energy