Mark Brouwer

UREA
1. Introduction

Urea [57-13-6] was discovered in urine by Rouelle in 1773 and first synthesized
from ammonia and cyanic acid by Wöhler in 1828. In 1870, urea was produced by
heating ammonium carbamate in a sealed tube.
Commercially, urea is produced by the direct dehydration of ammonium
carbamate, NH2 COONH4 , at elevated temperature and pressure. Mr. Carl Bosch
developed a chemical high pressure method during the establishment of the
new ammonia industry and was awarded the Nobel Prize in 1932. Ammonium
carbamate is obtained by direct reaction of ammonia and carbon dioxide. Urea’s
main use is as a fertilizer. Other applications are as a cattle-feed supplement, in
the manufacture of resins, glues, melamine, solvents, some medicinals, and in
reducing NOx emissions by catalytic reduction. Urea is classified as a nontoxic
compound.

2. Properties

Urea can be considered the amide of carbamic acid, NH2 COOH, or the diamide
of carbonic acid, CO(OH)2. At room temperature, urea is colorless, odorless,
and tasteless. Its properties are shown in Tables 1–4. Dissolved in water, it
hydrolyzes very slowly to ammonium carbamate (3) and eventually decomposes
to ammonia and carbon dioxide. This reaction is the basis for the use of urea as
fertilizer.
At atmospheric pressure and at its melting point, urea decomposes to
ammonia, biuret (1), cyanuric acid (2), ammelide (3), and triuret (4). Biuret is the
main and least desirable by-product present in commercial urea. An excessive
amount (>wt%) of biuret in fertilizer-grade urea is claimed to be detrimental to
plant growth.

O O

H2N N NH2
H
(1)
biuret

H
O N O

HN NH

O
(2)
cyanuric acid

Kirk-Othmer Encyclopedia of Chemical Technology. Copyright © 2019 John Wiley & Sons, Inc. All rights reserved.
DOI: 10.1002/0471238961.2118050113012218.a01.pub3
2 UREA

H
O N O

HN N

NH2
(3)
ammelide

O O O

H2N N N NH2
H H
(4)
triuret

Urea acts as a monobasic substance and forms salts with acids (4). With
nitric acid, it forms urea nitrate, CO(NH2 )2 ⋅HNO3 , which decomposes explo-
sively when heated. Solid urea is stable at room temperature and atmospheric
pressure. Heated under vacuum at its melting point, it sublimes without change.
At 180–190∘ C under vacuum, urea sublimes and is converted into ammonium
cyanate, NH4 OCN (5). When solid urea is rapidly heated in a stream of gaseous
ammonia at elevated temperature and at a pressure of several hundred kPa
(several atm), it sublimes completely and decomposes partially to cyanic acid,
HNCO, and ammonium cyanate. Solid urea dissolves in liquid ammonia and
forms the unstable compound urea–ammonia, CO(NH2 )2 NH3 , which decomposes
above 45∘ C (1). Urea–ammonia forms salts with alkali metals, for example,
NH2 CONHM or CO(NHM)2 . The conversion of urea into biuret is promoted by
low ammonia partial pressure, high temperature, and prolonged heating. At
10–20 MPa (100–200 atm), biuret gives urea when heated with ammonia (6,7).

Table 1. Properties of Urea

Property Value
melting point, ∘ C 133–134
index of refraction, n20 D 1.484, 1.602
density, d20
4
, g/cm3 1.3230
crystalline form and habit tetragonal, needles or prisms
free energy of formation, at −197.150
25∘ C, J/mola
heat of fusion, J/ga 251b
heat of solution in water, J/ga 243b
heat of crystallization, 70% 460b
aqueous urea solution, J/ga
bulk density, g/cm3 0.74
specific heat, J/(kg K)a
at 0∘ C 1.439
50 1.661
100 1.887
150c 2.109
a To convert J to cal, divide by 4.184.
b Endothermic.
c Exothermic.
 UREA 3

Table 2. Properties of Saturated Aqueous Solutions of Urea

Temperature, ∘ C Solubility in Density, Viscosity H2 O vapor
water, g/100 g g/cm3 mPa s(=cP) pressure, kPaa
solution
0 41.0 1.120 2.63 0.53
20 51.6 1.147 1.96 1.73
40 62.2 1.167 1.72 5.33
60 72.2 1.184 1.72 12.00
80 80.6 1.198 1.93 21.33
100 88.3 1.210 2.35 29.33
120 95.5 1.221 2.93 18.00
130 99.2 1.226 3.25 0.93
a To convert kPa into mm Hg, multiply by 7.5.

Table 3. Properties of Saturated Solutions in Urea in Ammoniaa

Temperature, ∘ C Urea in solution, wt % Vapor pressure
of solution, kPab
0 36 405
20 49 709
40 68 952
60 79 1094
80 84 1348
100 90 1267
120 96 507
a Source: Reproduced from Ref. 1.
b To convert kPa into atm, divide by 101.3.

Table 4. Properties of Saturated Solutions of Urea in Methanol and Ethanola

Temperature, ∘ C Methanol Ethanol
Urea, wt % Density, g/cm3 Urea, wt % Density, g/cm3
20 22 0.869 5.4 0.804
40 35 0.890 9.3 0.804
60 63 0.930 15.0 0.805
a Source: Reproduced from Ref. 2.

Urea reacts with silver nitrate, AgNO3 , in the presence of sodium hydroxide,
NaOH, and forms a diargentic derivative (5) of pale-yellow color. Sodium hydrox-
ide promotes the change of urea into the imidol form (6):

OAg

HN NH
Ag
(5)
4 UREA

OH

H2N NH
(6)

which then reacts with silver nitrate. Oxidizing agents in the presence of sodium
hydroxide convert urea into nitrogen and carbon dioxide. The latter reacts with
sodium hydroxide to form sodium carbonate (8):

NH2 CONH2 + 2NaOH + 3 NaOBr → N2 + 3NaBr + Na2 CO3 + 3H2 O

The reaction of urea with alcohols yields carbamic acid esters, commonly
called urethanes:
O O
NH2CNH2 + ROH NH2COR + NH3

Urea reacts with formaldehyde compounds such as monomethylolurea,

NH2 CONHCH2 OH, dimethylolurea, HOCH2 NHCONHCH2 OH, and others,
depending on the mol ratio of formaldehyde to urea and upon the pH of the solu-
tion. Hydrogen peroxide and urea give a white crystalline powder, urea peroxide,
CO(NH2 )2 ⋅H2 O2 , known under the trade name of Hypersol, an oxidizing agent.
Urea and malonic acid give barbituric acid (7), a key compound in medicinal
chemistry:
O OH
O
O O −2 H2O HN NH N N
+
H2N NH2 HOC COH O O HO OH

(7)
malonyl urea or
barbituric acid

3. Manufacture

Urea is produced from NH3 and CO2 at high pressure and temperature; both reac-
tants are obtained from an ammonia-synthesis plant. The latter is a by-product
stream, vented from the CO2 removal section of the ammonia-synthesis plant. The
two feed components are delivered to the high pressure urea synthesis section.
Depending on the feed mol ratio, the water content and parameters such as pres-
sure, temperature, and residence time, more or less carbamate is converted into
urea and water.
In case residence time is available, the formation of ammonium carbamate
and the dehydration to urea take place simultaneously, for all practical purposes:
O
2 NH3 + CO2 NH2CONH4
ammonium
carbamate (1)
 UREA 5

O O
NH2CONH4 NH2CNH2 + H2O
urea (2)

Reaction 1 is highly exothermic. The heat of reaction at 25∘ C and 101.3 kPa
(1 atm) is in the range of 159 kJ/mol (38 kcal/mol) of solid carbamate (9). The excess
heat is typically removed by producing steam. The rate and the equilibrium of
reaction 1 depend greatly upon pressure and temperature. This reaction may only
occur at a pressure that is below the pressure of ammonium carbamate at which
dissociation begins or, conversely, the operating pressure of the reactor must be
maintained above the vapor pressure of ammonium carbamate. The dissociation
pressure of pure carbamate has been investigated extensively (10–12), and the
average values are shown in Table 5.
Reaction 2 is endothermic by ca 31.4 kJ/mol (7.5 kcal/mol) of urea formed. It
takes place in the liquid phase.
Ammonium Carbamate. Ammonium carbamate is a white crystalline solid,
which is water soluble (1). It forms at room temperature by passing ammonia
gas over dry ice. In an aqueous solution at room temperature, it is slowly con-
verted into ammonium carbonate, (NH4 )2 CO3 , by the addition of one mol of water.
Above 60∘ C, the ammonium carbonate solution reverts to carbamate solution, and
at 100∘ C, only carbamate is present in the solution. Above 150∘ C, ammonium
carbamate loses a mol of water and forms urea. The specific heat of solid ammo-
nium carbamate is given in Table 6. Ammonium carbamate melts/dissociates at
ca 150∘ C and has a heat of fusion of ca 16.74 kJ/mol (4.0 kcal/mol). The conversion
of carbamate to urea begins at above 100∘ C. To obtain an appreciable amount of
urea at 100∘ C requires 20–30 h. The rate of conversion increases with increasing
temperature (13–15); at 185∘ C, ca 50% of the ammonium carbamate is converted
into urea in ca 30 min.
3.1. Conversion at Equilibrium. The maximum urea conversion at
equilibrium attainable at 185∘ C is ca 53% at infinite heating time. The conversion

Table 5. Vapor Pressure of Pure Ammonium Carbamate at which

Dissociation Begins
Temperature, ∘ C kPaa
40 31
60 106
80 314
100 861
120 2130
140 4660
160 9930
180 15,200; 19,300b
200 20,300; 36,500b
a To convert kPa into atm, divide by 101.3.
b The value has been extrapolated because, at temperatures above 170∘ C, the rate of reac-

tion (10) rapidly increases and it is difficult to determine the carbamate vapor pressure
owing to the formation of water and urea and the consequent lowering of the partial
pressure of ammonium carbamate.
6 UREA

Table 6. Specific Heat of Solid Ammonium Carbamate

Temperature, ∘ C J/(g K)a
20 1.67
60 1.92
100 2.18
140 2.43
180 2.59
a To convert J into cal, divide by 4.184.

Table 7. Reaction Equilibrium Constanta

Temperature, ∘ C Reaction equilibrium
constant, K
140 0.695
150 0.850
160 1.075
170 1.375
180 1.800
190 2.380
200 3.180
a Source: Reproduced from Ref. 16.

at equilibrium can be increased either by raising the reactor temperature or

by dehydrating ammonium carbamate in the presence of excess ammonia.
Excess ammonia shifts the reaction to the right side of the overall equation:
Water, however, has the opposite effect. Actual equilibrium constants at various
temperatures are given in Table 7. A detailed study of the effect of pressure on
urea conversion is given in Reference 17.

4. Processing

Currently, over 90% of all new urea plants are licensed by Saipem, Stamicarbon,
or Toyo Engineering Corporation (18,19). Saipem utilizes thermal stripping while
Stamicarbon and Toyo Engineering Corporation use CO2 stripping. Only these
three processes are here covered in detail.
The urea produced is typically either prilled or granulated. In some coun-
tries (currently mainly Europe and the United States), there is a market for liquid
urea–ammonium nitrate (UAN) solutions (32% N). In this case, a partial-recycle
stripping process is the best and cheapest system. The unconverted NH3 coming
from the stripped urea solution and the reactor off-gas is neutralized with
nitric acid. The ammonium nitrate solution formed and the urea solution from
the stripper bottom are mixed, resulting in a 32–35 wt% UAN solution. This
system drastically reduces investment costs as evaporation, finishing (prill or
granulation), and wastewater treatment are not required.
Future trends. There has been a steady increase in demand for urea.
All licensors have designed urea plants with increasingly higher capacities
driven by the economy of scale principle. Other trends in the urea process are
stricter environmental regulations and the production of urea product specialties
(multinutrient and higher efficiency urea fertilizer products).
 UREA 7

4.1. Saipem Snamprogetti (SAIPEM) Thermal Stripping Process.

The first industrial urea plant based on Snamprogetti (SAIPEM) Urea Technol-
ogy was put into operation in 1971. Since then more than 130 plants based on
this technology have been put in operation or are currently being implemented.
The Snamprogetti (SAIPEM) process is outlined in Figure 1. A differentiating
factor is that only heat is supplied to the stripper to remove unreacted NH3 and
CO2 from the urea solution coming from the reactor. Because of the relatively
high NH3 /CO2 ratio and the lower efficiency of this stripper, it is necessary to
have a medium (1.8 MPa, 18 bar) and low pressure (0.4 MPa, 4 bar) recirculation
section. The medium pressure section also contains a washing column (also
called MP absorber) to be able to recycle ammonia in pure form back to the
synthesis section. As there is a pure ammonia recycle, it means that the CO2
conversion in the synthesis is more important than the NH3 conversion. This is
because ammonia can be recycled without the need to add additional water to
the synthesis, and thus this recycle does not negatively influence the equilibrium
position of the urea formation reaction.
In the synthesis recycle loop, the stripped gas is going to one or two kettle
type high pressure carbamate condensers in series and to a high pressure separa-
tor and then back to the reactor. The flow is maintained by using an NH3 -driven
high pressure ejector. The reactor is operated at about 15 MPa (150 bar) with a
NH3 –CO2 molar feed ratio of about 3.5. The stripper is a falling-film type, and
since high temperatures (200–210∘ C) are required for efficient thermal stripping,
stainless steel tubing is not suitable. Titanium was initially used, but it was
also not satisfactory because of erosion issues. At this time, a bimetallic tube
of zirconium and 25-22-2 stainless steel or zirconium and titanium (OmegaBond
(SAIPEM)) is used.
High pressure Low pressure
Inert gas
Ammonia
Urea solution, carbamate, from BL Ammonia
carbon dioxide, ammonia receiver-
condenser
Carbamate
190° C
absorbers-
16 MPa Separator Carbamate condensers
N/C 3.6
H2O/CO2 Ammonia Vent Recycle
0.64 scrubbers
Carbon
Reactor dioxide
ammonia 86%

Preconcentrator
ST Evaporation
Ejector
ST ST Process
condensate
1st condenser treatment
0.5 MPa steam
Hydrolyzer
Air
Solution tankage
High pressure Low pressure
Stripper decomposer decomposer
Carbamate
condensers Urea for Treated
Carbon (2 vessels) prilling or process
dioxide 2nd condenser granulation condensates
0.34 MPa steam

Fig. 1. Snamprogretti™ thermal stripping urea process. BL = battery limits.

8 UREA

The stripper off-gas going to the high pressure carbamate condenser(s) is

mixed with the carbamate recycled from the medium and low pressure recircula-
tion sections. Both of these systems are similar to those shown in the total-recycle
process.
The plant is designed with an excellent heat-exchange system to keep overall
steam required to a minimum.
The plant wastewater containing NH3 and urea is subjected to a desorption–
hydrolysis operation to recover almost all the NH3 and urea. The hydrolyzer oper-
ates at 3–3.5 MPa (30–35 bar). It typically can be used as cooling water make-up
or boiler-feed water.
The urea solution is evaporated in a one or two-stage system depending on if
the final product is prills and the granulation technology that is applied to produce
granules.
Saipem lists the following as the strong points of the Snamprogetti
(SAIPEM) Urea Technology: A high efficient and reliable process (easy and safe
operation, high on-stream factor) along with a high quality product in terms of
biuret and moisture content. The design of medium pressure section, a buffer for
any upset in high pressure section, assures greater flexibility in plant operation.
Flexibility, excess of ammonia, and the possibility of blocking-in the high pressure
section assure a high on-stream factor (Reference 20, Saipem website).
4.2. Stamicarbon CO2 Stripping Process. In 1967, Stamicarbon revo-
lutionized the urea process by the invention of the HP CO2 stripper by Mr. Petrus
JC Kaasenbrood. The HP CO2 stripper led to the following three main benefits: (1)
the carbamate could be recycled at synthesis pressure so no extra water needed to
be added to recycle the carbamate; (2) no medium pressure recirculation section
was needed anymore; and (3) with the condensation of strip gases in the high pres-
sure carbamate condenser, low pressure steam could be produced, which could be
used in the downstream sections, reducing the steam consumption of a urea plant
of about a factor two.
The conventional total-recycle process scheme is shown in Figure 2, and the
Stamicarbon process schemes are presented in Figures 3–5.
The synthesis section of the first-generation CO2 stripping plant consists of
a reactor, stripper, falling-film high pressure carbamate condenser, and a high
pressure scrubber. In order to obtain a maximum urea yield per pass through the
reactor, a pressure of 14 MPa (140 bar) and a 2.95/1 NH3 —CO2 molar ratio are
maintained. The reactor effluent is distributed over the stripper tubes (falling-film
shell-and-tube exchanger) and contacted by the CO2 countercurrently. This causes
the partial NH3 pressure to decrease and the carbamate to decompose efficiently
at relatively low temperatures. The urea solution out of the stripper bottom can
therefore flow to a single-stage low pressure recirculation section (0.4 MPa, 4 bar).
There is no pure ammonia recycle in a Stamicarbon process, which means that
both the ammonia and the CO2 conversion in the synthesis are equally important.
The stripper off-gas is sent to the carbamate condenser. The carbamate
formed and noncondensed NH3 and CO2 are put into the reactor bottom and the
carbamate is converted into urea. The reactor is sized to allow enough residence
time for the reaction to approach equilibrium. The heat required for the urea
reaction and for heating the solution is supplied by additional condensation of
the gaseous NH3 and CO2 .
 Cooling
Cooling water
Separator water Ammonia
condenser Ammonia
Steam or recovery
Ammonia Ammonia
High Cooling condensate condensers
pressure water Ammonia reservoir
absorber preheater
High pressure
Condensate
absorber cooler Cooler
Equipment
High Ammonia To seal tank drainage
To seal tank pressure pump
High feed Ammonium
pressure carbamate
recycle Cooling water tank
feed pump Low pressure
absorber
cooler Ejector
Letdown Vent
Condenser
valve
Reactor Steam
Concentrator

Carbon
dioxide High pressure Steam
Steam
decomposer
Seal tank
Steam
Knock- Low pressure
out decomposer Product Product 75% Urea
drum seal tank tank solution
Compressor Reboiler

Fig. 2. Typical total-recycle urea process.

Inert gas
and ammonia

Scrubber 0.4 MPa

Carbon dioxide
ammonia
inerts

TCW Scrubber

Ammonia Ammonia water Gas

from BL
Ejector Carbamate recycle
0.5 MPa Steam Ammonia- Recycle
carbon dioxide-
water Carbon dioxide
and ammonia Flash gas
185°C Carbamate Evaporation
13.8 MPa Decomposer
condenser
N/C = 2.9 STM Process
Stripper condensate
Air treatment
STM
Reactor Hydrolyzer
TCW

72%

Urea solution

Carbon Urea for Treated

dioxide prilling or process
granulation condensates

Fig. 3. Stamicarbon CO2 stripping process. TCW = tempered cooling water.

10 UREA

Inerts

Carbamate

Urea Low
reactor pressure
steam
Scrubber Pool condenser
BFW
Steam
drum
NH3

Stripper

CO2
To recirculation
Fig. 4. Pool condenser synthesis section for Stamicarbon CO2 stripping process.

Inerts
High pressure
carbamate
pump

From high pressure

NH3 pump

Stripper

From CO2 To recirculation

compressor section
Fig. 5. Pool reactor synthesis section for Stamicarbon CO2 stripping process.

The noncondensable gases introduced in the CO2 (ie, passivation air) and
part of the unreacted NH3 and CO2 go to the high pressure scrubber, which typ-
ically consists of a shell-and-tube exchanger in the bottom portion and a packed
bed in the upper part. In the lower part, most of the NH3 and CO2 is condensed,
and the heat of condensation is dissipated in tempered cooling water. In the upper
part, the gases leaving the bottom section are countercurrently contacted with
carbamate solution recycled from recirculation. The scrubber off-gas, containing
nitrogen, oxygen, and very small amounts of NH3 and CO2 are vented to the
atmosphere after passing through an absorber.
 UREA 11

The carbamate solution from the scrubber flows to a high pressure ejector.
The NH3 feed pressure induces enough head to convey the carbamate solution
from the scrubber to the carbamate condenser.
The Stamicarbon wastewater system consisting of a desorber–hydrolyzer
and the hydrolyzer operates at 2 MPa (20 bar). It typically can be used as cooling
water make-up or boiler-feed water.
In 1994, Stamicarbon introduced the pool condenser in the synthesis section
(Fig. 4). The pool condenser replaces the falling-film vertical carbamate condenser
by a submerged horizontal carbamate condenser. This allowed a 34% decrease in
reactor volume and a 45% decrease in the carbamate condenser heat-exchange
area, thus reducing costs considerably for equipment, structural steel, and con-
struction.
In 1997, Stamicarbon introduced the pool reactor in the synthesis section
(Fig. 5). The horizontal pool reactor combines the pool condenser with the vertical
reactor and further simplified the urea synthesis section by further reducing the
number of high pressure equipment items from four to two.
The super duplex Safurex (Stamicarbon) steel enables high pressure vessels
and high pressure pipelines to be designed smaller, lighter, and more resistant to
corrosion.
In order to be more safe from a hydrogen explosion (sources: passivation
air, CO2, and NH3 ), a hydrogen removal system is installed in the CO2 feed, and
the high pressure scrubber and absorbers are designed with an expansion dome
and/or higher design pressures.
In 2018, Stamicarbon introduced the Ultra-Low Energy Design, which will
lead to a further 40% reduction in steam consumption in urea plants.
4.3. Toyo Engineering Corporation—ACES21 (TEC) Process.
Figure 6 shows the ACES21 (TEC) process synthesis section. The reactor, strip-
per, submerged vertical carbamate condenser, and ejector comprise the synthesis

To MP absorption
From cars. pump

Vertical
submerged
carbamate
condenser
(VSCC) Stripper
MP steam
Reactor

BFW LP
steam Cond
HP ejector

From NH3 pump To MP

decomposition
From CO2 comp
Fig. 6. TOYO’s ACES21 (TEC) synthesis process scheme. Source: Reproduced with per-
mission of Toyo Engineering Corporation.
12 UREA

section as major equipment (21). Liquid ammonia is fed into the reactor via the
ejector. Most of the CO2 is fed to the stripper as stripping media, and the rest is fed
to the reactor as a source of passivation air and a raw material for urea synthesis
in the reactor. Carbamate solution from the carbamate condenser is fed to the
reactor after being pumped by the ejector motive fluid high pressure liquid ammo-
nia. Urea synthesis solution leaving the reactor is fed to the stripper. Stripped
urea solution is sent to an MP recirculation stage. The stripped off-gas is fed to
the vertical submerged carbamate condenser. NH3 and CO2 gas condense to form
ammonium carbamate and urea in the shell side of the carbamate condenser. The
condensation heat is recovered to generate low pressure steam in the tube side.
Packed bed is provided at the top to absorb uncondensed NH3 and CO2 into recycle
carbamate solution from the MP absorption stage. Inert gas from top of the packed
bed is sent to the MP absorption stage. The driving force for liquid and gas circu-
lation in the synthesis loop is mainly provided by the ejector, while appropriate
elevation of the carbamate condenser supplies additional driving force by gravity.
As in all the processes, the process condensate and all other sources of waste
urea–NH3 –water contamination go to a desorber–hydrolyzer. It typically can be
used as cooling water make-up or boiler-feed water.
The super duplex DP28W steel enables high pressure vessels and high
pressure pipelines to be designed smaller, lighter, and more resistant to corrosion.
4.4. Other Processes. Flow sheets for typical partial-recycle process and
typical once-through urea process are given in Figures 7 and 8, respectively. A pro-
cess for urea production comprises a single reactor in the high pressure synthesis
section. These older type of processes have typically significant more energy con-
sumption figures than the modern urea process technologies. New grassroots urea

High pressure
Ammonia absorber

Water
Urea
reactor
Steam
Liquid High pressure High pressure
ammonia separator carbamate stripper
Off-gas to coproduct
Heater
synthesis
Gaseous
carbon dioxide
Steam
Low pressure
Heater carbamate stripper
Urea solution
(to finishing section)

Carbamate solution recycle

Fig. 7. Typical partial-recycle process.

 UREA 13

Off-gas (high pressure)

Effluent Off-gas (low pressure) To

coproduct
synthesis
Urea
reactor Steam Steam

Liquid Urea
ammonia solution To
finishing
High pressure Low pressure section
Gaseous
Carbamate strippers
carbon dioxide

Fig. 8. Typical once-through urea process.

technologies are developed and offered by Casale Switzerland, NIIK Russia, and
WEC and JX in China.

5. Finishing Processes

Urea processes provide an aqueous solution containing 70–85 wt% urea. This solu-
tion can be used directly for nitrogen fertilizer solutions such as UAN solution,
which is popular in certain areas (20). Urea solution can be concentrated by evap-
oration or crystallization for the preparation of granular compound fertilizers and
other products. Concentrated urea is solidified in essentially pure form as prills,
granules, pastilles, or crystals. Solid urea can be shipped, stored, distributed, and
used more economically than in solution. Furthermore, in the solid form, urea is
more stable.
5.1. Prilling. The manufacture of prills is somewhat decreasing especially
in export-oriented urea plants owing to the lower product quality compared to
granules. In a prilling plant, the urea solution from the recovery section is con-
centrated in two stages to 99.6 wt% urea melt. It is then pumped to the top of
a 60–110-m cylindrical concrete tower where it is fed into typically a spinning
bucket containing many (few thousands) small holes. The emerging small liquid
droplets solidify as they fall and are cooled by a forced or induced draft air flow. The
very fine dust that is formed for a major part by sublimation and exits at the top
of the tower with the air flow is an environmental problem. The quality problem
is that prill size must necessarily be small in order to obtain proper solidification
and cooling in the fall height that is practical. Generally, both the crushing and
impact strength of the prills are much less than for granules. This causes many
problems in handling both at the plant and in shipping. Stamicarbon has intro-
duced a “seeding” system that has improved the impact strength of the prills.
Also, formaldehyde can be added as it not only improves the crushing strength
somewhat but also suppresses the caking tendency in storage.
5.2. Granulation. Almost all new export-oriented urea plants produce
granules, and thyssenkrupp Fertilizer Technology (formerly Hydro-Agri) (22),
the Stamicarbon, the Toyo Engineering Corporation, and the Green Granulation
Technology (23) processes are used in the majority of plants (Figs. 9–12). The
 To atmosphere To atmosphere

Screens
Scrubber Scrubber
Recycle
to urea Process Crusher
solution unit water

Elevator
Granulator

Urea solution

Cooler

Cooler
To storage
Chiller

Air Air Air Air

Fig. 9. tkFT urea granulation process.

Bucket
elevator

Coarse
Urea granules
Fan Fan
Product
Hopper screen

Crusher
Fine Process
Product screen Scrubber water

Scrubber

Fluid-bed
granulator

Fluid-bed
cooler
Air
Recycle
heater

Formaldehyde

Scrubber
Fan Fan Fan circulation
Urea
pumps
Urea solution
pump Recycle
vessel

Fig. 10. Stamicarbon urea granulation process.

 Atm.

Screen

Product cooler
Recovered
urea
solution
Dust
scrubber Crusher

Granulator

Feed urea
solution
Air
Product
Air

Fig. 11. TOYO’s spout fluid bed granulation process. Source: Quoted under permission of
Toyo Engineering Corporation.

Process
water

Exhaust
air fan Stack
Scrubber
Recycle
pump

Granulator Crusher
Scrubbing
solution

Formaldehyde Atomization Screener

metering pump air blower

Final
Fluidization product
Urea melt air blower Elevator
pump
Fig. 12. Green granulation technology urea granulation process.
16 UREA

major differences between these various processes lie in the type of sprayers and
the movement of the fluid bed.
5.3. Rotoformer. IPCO (formerly Sandvik Process Systems) did develop
the urea forming pastillation technology with the Rotoform (IPCO) process repre-
senting an ideal solution for the solidification of molten urea and other fertilizers
(24). The high flexibility of the Rotoform (IPCO) system allows the production of
standard fertilizer urea as well as fertilizer specialties by mixing additives such
as ammonium sulfate, potassium chloride, zinc oxide, sulfur. The same equipment
can be used to produce urea of high purity for technical or pharmaceutical pur-
poses. Among the inherent benefits of the Rotoform (IPCO) process that make it
particularly suitable for urea pastillation are its low energy consumption and high
level of environmental friendliness. A typical capacity of one line is 125 mtpd.

6. Wastewater Treatment

For each mol of urea produced in a total-recycle urea process, 1 mol of water is
formed. It is usually separated from the urea melt in the evaporation section
of the plant. For example, a 1200 t/d plant discharges a minimum of 360 t/d of
wastewater.
Ammonia and small amounts of urea are usually found in the wastewater
because of entrainment carryover in the evaporation section.
The problem in reducing the NH3 and urea content in the wastewaters to
below 100 ppm is because it is difficult to remove one in the presence of the other.
The wastewater can be treated with caustic soda to volatilize NH3 . However, in
a more efficient method, urea is hydrolyzed to ammonium carbamate, which is
decomposed to NH3 and CO2 ; the gases are then stripped from the wastewater.
All process licensors also feature wastewater treatment technologies to
reduce ammonia and urea content to ppm levels.

7. Economic Aspects

Urea is used in all regions of the world and is widely traded in international mar-
kets due to its relatively cheap transport costs. There is a continuous growth in
global urea demand (and thus in production) due to among others the continu-
ous growth of number of people worldwide, the increasing consumption of meat.
According to the International Fertilizer Industry Association, urea production
reached nearly 200 × 106 metric tons per year in 2018.

8. Health, Environmental, and Safety Factors

8.1. Urea Process. Most safety hazards in a urea plant involve a release
of toxic ammonia, of which 90% can occur suddenly, without any prewarning
(25). Other main safety hazards are crystallization risks, vibration risks, back-
flow risks, hydrogen explosion risks, ammonium carbamate corrosion risks,
atmospheric corrosion, and corrosion under insulation risks.
 UREA 17

Ammonium Carbamate Corrosion Risks. Stainless steels can be used in

the urea synthesis because of the presence a protective oxide layer that mainly
consists of Cr2 O3 . This oxide layer, however, will slowly dissolve in hot carbamate
solution. The loss of this protective oxide layer is compensated by the oxidation
of chromium, in this way the oxide layer will be restored, that is why oxygen
continuously needs to be added to the carbamate solution.
The overall corrosion rate depends on the balance of these reactions: too little
oxidizing compared to the dissolution rate of the oxide layer results in a nonpro-
tective layer or even to active corrosion.
Ammonium carbamate solution behaves as an acid (Brönsted acid). Corro-
sion of stainless steels in urea synthesis is an acidic type of attack. In the absence
of oxygen, this will result in high (active) corrosion rates with hydrogen evolution.
High chromium content is beneficial: the more chromium in the stainless
steel, the higher the repassivation capacity and the lower the passive corrosion
rate will be.
8.2. Urea Product. Urea can be irritating to the skin, eyes, and the res-
piratory tract. Repeated or prolonged contact with urea in fertilizer form on the
skin may cause dermatitis. It is moderately toxic by intravenous and subcuta-
neous routes. High concentrations in the blood can be damaging. It reacts with
sodium hypochlorite to form explosive nitrogen trichloride. It is incompatible with
NaNO2 , P2 Cl5 , and nitrosyl perchlorate. Preparation of 15 N-labeled urea is haz-
ardous. When heated to decomposition, it emits toxic fumes of NOx (26).
The urea plants typically pay significant attention to limit their environ-
mental impact. However, the urea product applied as fertilizer currently does
not realize acceptable nitrogen use efficiency. A significant part of the nitrogen
is lost in the water and air, contributing to the formation of dead zones and to the
formation of greenhouse gases. The International Fertilizer Industry Association
actively combats this environmental impact through the site- and crop-specific
implementation of scientific management principles related to source, rate, tim-
ing, and placement (the 4Rs) of fertilizers (Source: IFA website).

9. Uses

9.1. Fertilizer. Nearly 90% of urea is consumed as fertilizer. Solid urea

containing 0.8–2.0 wt% biuret is primarily used for direct application to the
soil as a nitrogen-release fertilizer. Weak aqueous solutions of low biuret urea
(0.3 wt% biuret max) are used as plant food applied to foliage spray. Urea is
popular as a solid nitrogen fertilizer because of high N content (46%). Mixed
with additives, urea is used in solid fertilizers of various formulations, for
example, urea–ammonium phosphate (UAP), urea–ammonium sulfate (UAS),
and urea–phosphate (urea + phosphoric acid). Concentrated solutions of UAN
solutions (80–85 wt%) have a high nitrogen content but low crystallization
point, suitable for easy transportation, pipeline distribution, and direct spray
application.
9.2. NOx Emissions Reduction. A growing use for urea is a process
called selective catalytic reduction to reduce NOx emissions from diesel engines.
18 UREA

Urea solution is sprayed into the engines or burners exhaust where it converts
the nitrogen oxides to nitrogen and water.
9.3. Animal Feeds. Urea is also used as feed supplement for ruminants,
where it assists in the utilization of protein. Urea is used in the preparation of
lysine, an amino acid, widely used in poultry feeds.
9.4. Resins. Urea is one of the raw materials for urea–formaldehyde
resins. These resins are produced by the condensation reaction between urea
and formaldehyde. These resins have found outlets in adhesives for paper, board,
plywood, surface coatings, molding resins, and textile processing. They are also
used to coat textiles, paper, and leather (27,28). Urea (with ammonia) pyrolyzes
at high temperature and pressure to form melamine–formaldehyde resins. These
resins are used as adhesives, paints, laminates, molding compounds and for
coating paper and textiles (27).
9.5. Clathrates. Reagent-grade urea is used in some pharmaceutical
preparations. Urea has a remarkable property of forming crystalline complexes
or adducts with straight-chain organic compounds. These crystalline complexes
consist of a hollow channel, formed by the crystallized urea molecules, in
which the hydrocarbon is completely occluded. Such compounds are known as
clathrates. The type of hydrocarbon occluded, on the basis of its chain length, is
determined by the temperature at which the clathrate is formed. This property
of urea clathrates is widely used in the petroleum-refining industry for the
production of jet aviation fuels and for dewaxing of lubricant oil. The clathrates
are broken down by simply dissolving urea in water or in alcohol.
9.6. Others. Urea is used in some pesticides, as a viscosity modifier for
casein or starch-based paper, coatings, pharmaceuticals, pesticides, toothpaste,
cosmetics, flame-proofing agents, and fabric softeners.

BIBLIOGRAPHY

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Mavrovic, Consulting Engineer; “Urea” in ECT 3rd ed., Vol. 23, pp. 548–575, by
Ivo Mavrovic, Consultant and A. Ray Shirley, Jr., Applied Chemical Technology;
in ECT 4th ed., Suppl. Vol., pp. 597–621, by Ivo Mavrovic, Consultant, A. Ray
Shirley, Jr., Applied Chemical Technology, G. R. “Buck” Coleman, Consultant.

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MARK BROUWER
UreaKnowHow.com B.V., Maastricht, the
Netherlands