INTRODUCTION

2.1 INTRODUCTION TO UREA

Urea is a nitrogenous compound with osmotic diuretic activity that contains a carbonyl group
bound to two amine groups. Urea is the end product of protein metabolism and is created in
the liver by the urea cycle from ammonia. The administration of urea raises the osmolality of
blood plasma, allowing more water to flow from tissues such as the brain, cerebrospinal fluid,
and eye into interstitial fluid and plasma, lowering pressure in those tissues and increasing
urine production.

Urea, also known as carbamide, is the carbonic acid diamide. H2NCONH2 is the formula.
Urea is used as a fertiliser and feed supplement, as well as a raw material to produce plastics
and pharmaceuticals. It is a colourless, crystalline substance that melts at 132.7 oC (271 oF)
and decomposes before boiling.

2.2 HISTORY OF UREA

Rouelle le cadet is recognized as the first person who seperate the urea from urine in 1773,
when it was in a very impure condition. However, as Backer pointed out in 1943, credit for
this discovery goes unmistakably to Herman Boerhaave (1668-1738), who prepared urea (or
its addition compound with sodium chloride) from urine some time before 1727. There's
every reason to believe Boerhaave's specimen was genuine. more pure than the one
mentioned by Rouelle over 50 years later, or the one obtained by Fourcroy and Vauquelin
during their first research in 1799
2.3 PROPERTIES OF UREA

2.3.1 CHEMICAL PROPERTIES OF UREA

Molecular weight 60.05

Relative humidity 60%
Maximum nitrogen content 46.6%
Specific gravity 1.335
Heat of fusion 60 Cal/gm (endothermic)
Heat of solution, in water 58 Cal/gm (endothermic)
Bulk density 0.74 gm/cc

2.3.2 PHYSICAL PROPERTIES

Urea is a white, odourless, hygroscopic acid. It is non-corrosive.

2.4 The Synthesis of urea

In any process involving urea production, the underlying principle remains the same with
these two reactions below:

Kcal
1) CO2 + 2NH3 NH2COONH4 ∆ H =−37.4 mol
gm
Kcal
2) NH2COONH4 NH2CONH2 + H2O ∆ H =+6.3 mol
gm

Undesirable side reaction:

1) 2NH2CONH2 NH2CONHCONH2 + NH3

(biuret)
Urea is a well-known chemical substance that is used as a fertiliser and polymer raw material
(Haynes & Naidu, 1998). In recent years, urea has drawn interest as a solid-state energy
carrier. Carbon dioxide and ammonia (from the Haber process) are widely used to make urea
(Krase & Gaddy, 1922). The reaction takes place at 150°C and 2 MPa, and the urea-synthesis
plant can be maintained due to its proximity to the ammonia-synthesis plant, from which it
gets most of its input energy. Because of these energy factors, the traditional energy-intensive
urea synthesis method is not appropriate for ammonia use in the environment. However,
since nitrogen in recovered ammonium ion does not have an extreme strong triple bond like
N2, there is no need for additional energy to divide the N2 bond as in the Haber process,
which is an advantage over the traditional urea synthesis method. Since one of the goals of
environmental ammonia use is to minimise ammonia treatment energy, it is important for the
urea synthesis reaction to reduce input energy in order to be accepted by society (Manaka et
al., 2020)
5.0 PROCESS EQUIPMENT

5.1 REACTOR

In the process, inside the reactor, when liquid ammonia was compressed with CO 2 at high
temperature and pressure will produce urea in two forms;

2NH3 + CO2 ⇔ NH2COONH4

NH2COONH4 ⇔ NH2CONH2 + H2O

Both reactions are reversible as only partial conversion occurs in the reactor. In the reactor,
the NH3 & gaseous CO2 react to form ammonia Carbamate which a portion of which
dehydrates to form urea & water. The fraction of Carbamate that dehydrates is determine by
the ratio of various reactants, operating temperature, the residence time in the reactor and

NH 3
reaction pressure. The mole reaction of CO 2 is around 2 : 1 . The mole ration to CO is
2

around 0.67: 1.

In the synthesis conditions (T=180°C, P=188 atms), the first reaction occur rapidly and is
completed. The second reaction occurs slowly and determined the reactor volume. Urea
reactor is a plug flow type with 10 no.s sieve trays to avoid back mixing and to avoid escape
where stripping occur of NH3 favours decomposition of carbamate, and 80% of carbamate is
decomposed here. The pressure inside the stripper is the same as the reactor.

Kcal
NH2COONH4 (s) 2NH3 (g) + CO2 (g) Δ H = +37.4 gm−mole

This reaction involves increase in volume and absorption of heat, this this reaction will be
favoured by decrease in pressure and increase in temperature. Plus, decreasing the partial
pressure of either of the products will also favour the forward reaction. The process based on
first principle of decrease in pressure and decrease in temperature is called conventional
process whereas process based on increase/decrease of partial pressure of NH 3 or CO2 is
called stripping process. According the above equation, we have;

K = (pNH3)2*(pCO2) [ where, K= equilibrium constant

5.2 THE STRIPPER

The stripping is affected at synthesis pressure itself using CO 2 or NH3 as stripping agent. If
CO2 is selected, it is to supplied to the decomposer or stripper. While if NH 3 is selected it is to
be obtained from the system itself because excess NH3 is present in the reactor as in
Snamprogetti’s process. CO2 stripping is advantageous because introducing CO2 increase p
CO2. So, pNH3 will be reduced to maintain P constant as

P = pCO2 + pNH3.

At a particular temp K is constant so when pNH 3 is reduced to keep K constant, carbamate

will be reduced faster by decomposition as pNH3 appears in the equilibrium equation with a
power of two. Selection of 1 st stage decomposition should be in such was that minimizes
water from evaporates because the recovered gases go along with the carbamate to reactor
again and if water enters reactor again, the production will be affected adversely due to
hydrolysis of urea. (“THE SNAMPROGETTI Contents,” n.d.)
5.3 CARBAMATE CONDENSER

The main usage of Carbamate Condenser is to cool ammonia feed and the gases from the
stripper that mainly CO2. Their ammonia and carbon dioxide combined again to from
ammonium carbamate, which then will be passed again to the reactor to convert it to urea.
The traditional high pressure carbamate condenser is a vertical shell and tube exchanger with
process medium on the tube idea. Ammonium carbamate wash solution from the scrubber,
which recover residual ammonia and carbon dioxide from the inert gas purge from synthesis
loop. The overhead gases from stripper and the recovered solution from medium pressure
absorber all then flow to the high pressure carbamate condenser through mixer where total
mixture except for a few inerts is condensed and recycled back to the reactor by carbamate
ejector. Condensing the gases at high temperature and pressure permits the recovery of
condensation heat in the production of steam at 4.5 atms in high pressure carbamate
condenser. From top of carbamate separator, the incondensable gases come out consisting of
inerts and little quantity of NH3 and CO2 unreacted in the condenser. The unreacted reactants
then are sent to the bottom of Medium Pressure Decomposer (MP Decomposer). (“THE
SNAMPROGETTI Contents,” n.d.)
5.4 MEDIUM PRESSURE DECOMPOSER (MP DECOMPOSER)

In this section, the main target is to partially strip out the reactants (ammonia and carbon
dioxide) from the urea solution. The removal is done by condensation in water, recycled them
back to the reactor, together with ammonia and carbon dioxide aqueous solution collected
from the downstream section of the plant. A distillation column is prepared in this section to
separate excess ammonia and recycled back to the reactor separately. This column operates at
about 17 bar. Snamprogetti added a particular feature of another partial condensation of the
removal ammonia and carbon dioxide in a shell of preheater within vacuum section,
recovering some energy in the form of 200 kg of steam per ton of urea. Aside from the
feature, another advance technology of inerts washing. Inerts such as CO, H 2 and CH4,
contained mainly in the carbon dioxide and passivation air, though quantity of passivation air
resulted is considered little compared to other type of plants. Here, the washing inerts defines
as recovering ammonia in the inerts. For the complete abatement of the ammonia contained
in the inerts, in completely safe conditions with regard to explosions, Snamprogetti has
patented a washing method that has already been applied in some plants. This consists of
washing the inerts with water after the addition of a quantity of flammable gas, as for
example natural gas, in such an amount that after the ammonia has been eliminated, the
composition of the inerts is out of the explosive field due to the excess of flammable gas. The
washed inerts are sent to a burner together with the natural gas (“THE SNAMPROGETTI
Contents,” n.d.)
Image 1: Safe Ammonia Washing from “Inerts” [Process of inerts washing- ammonia recoveration]. (2014). Retrieved May
4, 2017, from http://www.saipem.com/static/documents/spm_UREAri_L02_14_01_10.pdf

5.5 LOW PRESSURE DECOMPOSER (LP DECOMPOSER)

From Saipem’s booklet of The Snamprogetti Urea Technology, it is summarised that the low
pressure decomposer, falling film type of decomposer, has the main purpose of to further
purify and recover undesired product in the urea solution flowing from previous process of
MP decomposer. Before entering LP decomposer, the flowing urea solution is first expanded
at 4.5 atms. Flowing into the LP decomposer, the solution passes through two parts of top
separator and decomposition section. Similarly, in the MP decomposer, the top separator
function as to remove any released flash gases (gas- form refrigerant; spontaneously
produced when condensed liquid subjected to boiling), from entering the tube bundle. Passes
through the top separator, the decomposition section then performs the decomposition of any
residual carbamate, and also the condensation of residual carbon dioxide and ammonia, to be
removed and recycle back to the reactor (“THE SNAMPROGETTI Contents,” n.d.)

5. 6 VACUUM CONCENTRATION (EVAPORATOR)

Upon leaving the LP section, the urea solution then enters this section with the target process
of concentrating, again, removing any residual of carbon dioxide, ammonia, although their
presence is small in quantities. This final concentration process is made under vacuum in two
steps at 0.3 and 0.03 atms respectively, for the formation of prilled product and granular
product, according to the granulation technology used. The necessary heat has been provided
thru partial condensation of the vapours from the MP section. This section also provides the
solution of lump formation problem that occur during second vacuum separator. The
prevention of lump formation is by wetting the internal walls of the separator, a small
recycling of molten urea process. Water condensation also introduced in this section where
Snamprogetti succeed in discharging large amount of process water with 1 ppm of urea and 1
ppm of ammonia and simultaneously, reutilize the process water as BFW, in order to
minimise energy consumption (“THE SNAMPROGETTI Contents,” n.d.)
5.7 PRILLING (FINISHING SECTION)

In this final section, the final product of 98% molten urea will be converted to pellets. Prilling
is the method of producing reasonably uniform spherical particles from molten solids, strong
solutions or slurries, (Walters. J. K. 2011, February) which in this case, pellets. Molten urea
(99.8% b.w.) is sprayed at the top of the prilling tower, at a height of 55-80 m, according to
climatic conditions; at the bottom, essentially spheroidal urea particles, namely prills, are
collected and sufficiently cooled in order to be sent to storage or directly to the bagging
section without screening, coating or any other treatment. Certain plant owners have
requested the additional of formaldehyde (an organic compound- aldehyde) to the molten
urea just before entering this section. The purpose is to improve the free-flowing
characteristics of the prilled urea and to achieve a slight increase in hardness. Additionally, a
cooling medium is formed upon the rising draught of air inside the prilling which removes
the solidification heat and cools the prills. Unfortunately, the prilling tower top’s design has
come up with environmental hazard of too much air entrain too much of urea dust. This
represents a serious pollution problem. With regard to this issue, Snamprogetti has patented a
dedusting system, which manage to reduce urea dust from 40 to 15 mg/Nm3of air. Aside
from urea dust, the presence of ammonia entertains the similar issue. Hence to abate
ammonia, Snamprogetti came up with the solution of washing the air with slight acidified
acid which is done just before the prilling tower. The addition of an inorganic acid to the urea
melt (solution) drastically reduces ammonia quantity in the air from the prilling tower. The
values obtained are 20-70 mg/Nm3. Fortunately, side result from this process is that ammonia
quantity in the prills is greatly reduced and also drastic reduction in the presence of ammonia
in the work environment (conveyor belt chutes, storage). (“THE SNAMPROGETTI
Contents,” n.d.)
REFERENCES

Haynes, R. J., & Naidu, R. (1998). Influence of lime, fertilizer and manure applications on
soil organic matter. Nutrient Cycling in Agroecosystems, 51(123), 123–137.
http://link.springer.com/article/10.1023/A:1009738307837

Krase, N. W., & Gaddy, V. L. (1922). Synthesis of Urea from Ammonia and Carbon Dioxide.
Industrial and Engineering Chemistry, 14(7), 611–615.
https://doi.org/10.1021/ie50151a009

Manaka, Y., Nagatsuka, Y., & Motokura, K. (2020). Organic bases catalyze the synthesis of
urea from ammonium salts derived from recovered environmental ammonia. Scientific
Reports, 10(1), 1–8. https://doi.org/10.1038/s41598-020-59795-6

THE SNAMPROGETTI Contents. (n.d.). The Snamprogetti Urea Process.