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Urea Process Technical Report PDF
Urea Process Technical Report PDF
Faculty of Engineering
Chemical Engineering Department
UAN Project
Urea Ammonium Nitrate
Abstract
This report is represented from group 2 working on Urea Ammonium Nitrate production
project, The report give a general overview on the different aspects of the project, starting
from the history of product and how it was discovered going through its physical and
chemical properties that is really important to know the appropriate way of handling and
using of the both the raw materials and the product.
The report also discuss the main theory of producing Urea which is the main product we
focus on through our report and also the different processes and technologies used in its
production, where so many processes were developed with different technologies
(different conditions of reaction) which are discussed in a general overview in this report,
the processes are Stamicarbon process, Snamprogitti process and ASEC process.
Different aspects like economical and environmental are also covered.
II
Contents
Abstract
II
Table of contents
III
Table of Figures
Introduction
1. Fertilizers
1.1 Forms
1.2 Main elements used in in-organic (manmade) fertilizers industry
1.3 Problems with in-organic fertilizers
1.4 Urea
2. History
3.
4.
5.
6.
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6
7
7
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11
13
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IV
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42
Table of Figures
Page
Fig 0
Synthesis gas
10
Fig 1
14
Fig 2
15
Fig 3
16
Fig 4
16
Fig 5
16
Fig 6
16
Fig 7
17
Fig 8
17
Fig 9
Fig 10
17
18
Fig 11
18
Fig 12
20
Fig 13
21
Fig 14
21
Fig 15
24
Fig 16
25
Fig 17
27
Fig 18
29
Fig 19
31
Fig 20
32
Fig 21
32
Table 1
Table 2
Table 3
Table 4
Tables
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11
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Introduction
1. Fertilizer
Fertilizer (or fertiliser) is any organic or inorganic material of natural or synthetic origin
(other than liming materials) that is added to a soil to supply one or more plant nutrients
essential to the growth of plants .A recent assessment found that about 40 to 60% of crop
yields are attributable to commercial fertilizer use. Mined inorganic fertilizers have been
used for many centuries, whereas chemically synthesized inorganic fertilizers were only
widely developed during the industrial revolution.
1.1 Forms
Fertilizers come in various forms. The most typical form is granular fertilizer (powder
form). The next most common form is liquid fertilizer; some advantages of liquid
fertilizer are its immediate effect and wide coverage. There are also slow-release
fertilizers (various forms including fertilizer spikes, tabs, etc.) which reduce the problem
of "burning" the plants due to excess nitrogen.
More recently, organic fertilizer is on the rise as people are resorting to environmental
friendly (or 'green') products. Although organic fertilizer usually contain less nutrients,
some people still prefer organic due to natural ingredients
1.2 Main Elements used in in-organic (manmade) Fertilizers industries;
Phosphorus
Nitrogen
Calcium
Potassium
Magnesium
Sulphur
1.4 Urea;
The highest fixed nitrogen-containing fertilizer 46.7 wt %, urea is a white solid that is
soluble in water and alcohol. It is usually sold in the form of crystals, prills, flakes, or
granules. Urea is an active compound that reacts with many reagents. It forms adducts
and clathrates with many substances such as phenol and salicylic acid. Urea is gaining
greater acceptance as a slow rate fertilizer.
6
2. History
2.1 Production of ammonia:
Ammonia was made for the first time in 1774 and by 1785 its exact composition was
determined. Nitric acid, known earlier, was synthesized for the first time and by 1771 it
was being produced commercially.
Urea was identified in 1773 and in 1775 the presence of large amounts of calcium
phosphate in bones was confirmed. In 1784, the chemical nature of water was discovered.
The Haber process is a method of producing ammonia developed in WWI. The Germans
needed nitrogen to for making their explosives. When the Allies blocked off all trade
routes going to and from Germany, they lost all source of sodium nitrate and potassium
nitrate, their source of nitrogen. They found their source of nitrogen in the air, which was
80% nitrogen. The chemist Fritz Haber developed the Haber Process in WWI, which
takes molecular nitrogen from the air and combines it with molecular hydrogen to form
ammonia gas, which the chemical formula is NH3.The equation for the reversible
reaction;
N2(g) + 3H2(g)
2NH3(g) + 92 kJ.
in 1960. Expansion in urea capacity slowed between 1960 and 1975, eventually reaching
3 million tons at the end of this period. By 1980, production of fertilizer urea was 7.2
million tons, 60 percent of it in solid form. In 1960, 75 percent of the total urea cont
primary urea solutions produced at anhydrous ammonia plants was utilized as fertilizer
and by 1982 this usage had increased to 92 percent. Urea consumption in 1994 accounted
for 14.7 percent of the 12.6 million tons of nitrogen applied to U.S. croplands.
3. Uses of Urea
1. The major use of urea is the fertilizer field, which accounts for approximately 80% of
its production (about 16.2 billion pounds were produced during 1994 in U.S.). About
10% of urea is used for the production of adhesives and plastics (Urea formaldehyde).
2. Urea possesses a unique property of forming adducts with n-paraffins. This is used in
separating C12-C14 n-paraffins from kerosene for detergent production
3. The nucleophilic addition reaction of urea to formaldehyde produces mainly
monomethylol urea and some dimethylol urea. When the mixture is heated in presence of
an acid, condensation occurs, and water is released, it produces an important commercial
polymer (urea formaldehyde resins) that is used as glue for particle board and plywood.
4. Explosive; Urea can be used to make urea nitrate, a high explosive which is used
industrially and as part of some improvised explosive devices
5. Automobile systems; Urea is used in SNCR and SCR reactions to reduce the NO x
pollutants in exhaust gases from combustion from diesel, dual fuel, and lean-burn natural
gas engines. The BlueTec system, for example, injects water-based urea solution into the
exhaust system. The ammonia produced by the hydrolysis of the urea reacts with the
nitrogen oxide emissions and is converted into nitrogen and water.
6. Also used as a stabilizer in nitrocellulose explosives
7. A component of animal feed, providing a relatively cheap source of nitrogen to
promote growth.
8. A non-corroding alternative to rock salt for road de-icing, and the resurfacing of
snowboarding half pipes and terrain parks
9. A flavor-enhancing additive for cigarettes
10. A main ingredient in hair removers such as Nair and Vet.
11. A browning agent in factory-produced pretzels
12. An ingredient in some skin creams, moisturizers, hair conditioners
13. A reactant in some ready-to-use cold compresses for first-aid use, due to the
endothermic reaction it creates when mixed with water.
14. A cloud seeding agent, along with other salts.
15. A flame-proofing agent, commonly used in dry chemical fire extinguisher charges
such as the urea-potassium bicarbonate mixture.
16. An ingredient in many tooth whitening products.
17. Along with ammonium phosphate, as a yeast nutrient, for fermentation of sugars into
ethanol.
18. A nutrient used by plankton in ocean nourishment experiments for geo-engineering
purposes.
19. As an additive to extend the working temperature and open time of hide glue
20. As a solubility-enhancing and moisture-retaining additive to dye baths for textile
dyeing or printing
21. Urea can be used to make urea nitrate, a high explosive which is used industrially and
as part of some improvised explosive devices.
Synthesis gas is a major source of hydrogen, which is used for producing ammonia.
Ammonia is the host of many chemicals such as urea, ammonium nitrate and
hydrazine. Carbon dioxide, a by-product from synthesis gas reacts with ammonia to
produce urea.
10
1.439
1.661
1.887
2.109
0
20
40
60
80
100
120
Solubility
in Water
(g/100 g
Solution
41.0
51.6
62.2
72.2
80.6
88.3
95.5
130
99.2
Density
(g/cm3)
1.120
1.147
1.167
1.184
1.198
1.210
1.22 1
Viscosity
(mPa-s =
cP)
2.63
1.96
1.72
1.72
1.93
2.35
2.93
1.226
Water
Vapor
Pressure
(kPa)
0.53
1.73
5.33
12.00
2 1.33
29.33
18.00
3.25
0.93
Solvent
Ammonia
Methanol
Ethanol
0
34.9
13.0
2.5
Temperature
40
60
67.2
78.7
26.1
38.6
8.5
13.1
20
48.6
18.0
5.1
12
80
84.5
100
90.4
5. Production
5.1 General Theory;
Step 1 Synthesis
A mixture of compressed CO2 and ammonia is reacted to form ammonium carbamate.
This is an exothermic reaction, and heat is recovered by a boiler which produces steam.
The first reactor achieves 78% conversion of the carbon dioxide to urea and the liquid is
then purified. The second reactor receives the gas from the first reactor and recycles
solution.
Step 2 Purification
The major impurities in the mixture at this stage are water from the urea production
reaction and unconsumed reactants (ammonia, carbon dioxide and ammonium
carbamate). The unconsumed reactants are removed in three stages3. Firstly, the pressure
is reduced and then the solution is heated, which causes the ammonium carbamate to
decompose to ammonia and carbon dioxide:
NH2COONH4
2NH3 + CO2
At the same time, some of the ammonia and carbon dioxide flash off. The pressure is then
reduced on two other stages, with more ammonia and carbon dioxide being lost at each
stage. By the time the mixture is at -0.35 bar gauge a solution of urea dissolved in water
and free of other impurities remains.
At each stage the unconsumed reactants are absorbed into a water solution which is
recycled to the secondary reactor. The excess ammonia is purified and used as feedstock
to the primary reactor.
Step 3 Concentration
75% of the urea solution is heated under vacuum, which evaporates off some of the
water, increasing the urea concentration from 68% w/w to 80% w/w. At this stage some
urea crystals also form. The solution is then heated again to dissolve these crystals prior
to evaporation. In the evaporation stage molten urea (99% w/w) is produced at 140oC.
Step 4 Granulation
Urea is sold for fertilizer as 2 4 mm diameter granules. These granules are formed by
spraying molten urea onto seed granules which are supported on a bed of air. This occurs
in a granulator which receives the seed granules at one end and discharges enlarged
granules at the other as molten urea is sprayed through nozzles. Dry, cool granules are
classified using screens. Oversized granules are crushed and combined with undersized
ones for use as seed.
All dust and air from the granulator is removed by a fan into a dust scrubber, which
removes the urea with a water solution then discharges the air to the atmosphere. The
final product is cooled in air, weighed and conveyed to bulk storage ready for sale.
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5.3 Principles
Chemical Equilibrium (1);
In all commercial processes, urea is produced by reacting ammonia and carbon dioxide at
elevated temperature and pressure according to the Basaroff reactions:
2NH3 (l) +CO2 (l)
NH2COONH4
(1)
H =117 kJ/mol
NH2COONH4
In the first reaction, carbon dioxide and ammonia are converted to ammonium
carbamate; the reaction is fast and exothermic.
In the second reaction which is slow and endothermic, ammonium carbamate
dehydrates to produce urea and water.
Since more heat is produced in the first reaction than consumed in the second the
overall reaction is exothermic.
-A schematic of the overall process and the physical and chemical equilibrium
involved is shown followed;
a maximum (Figs 3 and 4). This effect is usually attributed to the fact that the ammonium
carbamate concentration as a function of temperature goes through a maximum. This
maximum in the ammonium carbamate concentration can be explained, at least
qualitatively, by the respective heat effects of Reactions (1) and (2).However, this
mechanism cannot explain the observed conversion maximum fully and quantitatively;
other contributing mechanisms have been suggested.
16
Fig 9 Urea yield in the liquid phase at chemical equilibrium as a function of temperature NH3: CO2 ratio = 3.5 mol/mol (initial
mixture); H2O: CO2 ratio = 0.25 mol/mol (initial mixture)
17
Fig 10 Urea yield in the liquid phase at chemical equilibrium as a function of H 2O:CO2 ratio T=190 C NH3:CO2 ratio
= 3.5 mol/mol (initial mixture)
Ultimately, project economics (investment and consumptions) will dictate the choice of process
parameters in the reaction section. Without going into such time- and place-dependent economic
considerations, one can argue that the urea yield (i.e., the concentration of urea in the liquid
phase) is a better tool for judging optimum process parameters than CO 2 or NH3 conversion.
Figure 8 illustrates that urea yield as a function of temperature also goes through a maximum; the
location of this maximum is of course composition dependent. Figure 9 again shows the
detrimental effect of excess water on urea yield; thus, one of the targets in designing a recycle
system must be to minimize water recycle. Figure 10 shows that the urea yields as a function of
NH3:CO2 ratio reaches a maximum somewhat above the stoichiometric ratio (2:1). This is one of
the reasons that all commercial processes operate at NH3:CO2 ratios above the stoichiometric
ratio. Another important reason for this can be found from the physical phase equilibrium in the
NH3 CO2 H2O urea system
Fig 11 Urea yield in the liquid phase at chemical equilibrium as a function of NH3:CO2 ratio T=190 C; H2O: CO2
ratio = 0.25 mol/mol (initial mixture)
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ii.
simultaneously. The off-gas from this first decomposition step was subjected to
rectification, from which relatively pure NH3 (at the top) and a bottom product
consisting of an aqueous ammonium carbamate solution were obtained. Both
products are recycled separately to the urea reactor. In these processes, all
unconverted CO2 was recycled as an aqueous solution, whereas the main portion
of unconverted NH3 was recycled without an associated water recycle. Because
of the detrimental effect of water on reaction conversion, achieving a minimum
CO2 recycle (and thus maximum CO2 conversion per reaction pass) was much
more important than achieving a low NH3 recycle. All conventional processes
therefore typically operate at high NH3:CO2 ratios (45 mol/mol) to maximize
CO2 conversion per pass. Although some of these conventional processes, partly
equipped with ingenious heat-exchanging networks, have survived until now (see
Section 4.3.1), their importance decreased rapidly as the so-called stripping
processes were developed.
iii.
Stripping Processes.
In the 1960s, the Stamicarbon CO2-stripping process was developed, followed later by
other processes (in Section 3.3.2). Characteristic of these processes is that the major part
of the recycle of both unconverted NH3 and unconverted CO2 occurs via the gas phase;
such that none of these recycles is associated with large water recycles to the synthesis
zone. Another characteristic difference between conventional and stripping processes in
terms of the recycle scheme can be found in the way of which heat is supplied to the
recirculation zones. The energy balance of the conventional processes is shown in Figure
12. In this first-generation urea process, the heat supplied to the urea synthesis solution
was used only once; therefore, this type of process can be referred to as an N = 1 process.
Such a process required about 1.8 t of steam per ton of urea.
20
Fig 13 Conceptual diagram of the heat balance of a conventional urea process Heat to each subsequent heater is
supplied in the form of steam; the heat is used only once (N = 1).
The energy balance of a stripping plant is shown in Figure 13. As in conventional plants,
heat must be supplied to the urea synthesis solution to decompose unconverted carbamate
and to evaporate excess ammonia and water. However, a distinct difference in the heat
balance with respect to the conventional process is that only the heat in the first heater
(the high-pressure stripper) is imported. This heat is recovered in a high pressure
carbamate condenser (unconverted ammonia and carbon dioxide are condensed to form
ammonium carbamate) and reused in the low pressure heaters. The heat supplied is
effectively used twice; thus, the term N =2 process is used. The average energy
consumption of the stripping process is 0.8 1.0 t of steam per ton of urea.
5.4.2. Corrosion
Urea synthesis solutions are very corrosive. Generally, ammonium carbamate is
considered the aggressive component. This follows from the observation that carbamatecontaining product streams are corrosive whereas pure urea solutions are not. The
corrosiveness of the synthesis solution has forced urea manufacturers to set very strict
demands on the quality and composition of construction materials. Awareness of the
important factors in material selection, equipment manufacture and inspection,
technological design and proper operations of the plant, together with periodic
inspections and nondestructive testing are the key factors for safe operation for many
years Corrosion protection is achieved by the use of well proven design principles,
stringent material and fabrication specifications, complemented by detailed codes of
21
practice for operating, monitoring and inspecting equipment. The corrosiveness at a given
point in the plant is determined by the temperature, the process components, the
concentration of dissolved oxygen and the presence of contaminants that may accelerate
corrosion. The formation on start-up and maintenance of a passive oxide layer on
stainless steel surfaces is of the utmost importance. Stainless steel lined carbon steel
vessels are usually used in the HP synthesis section for economic reasons, including leak
detection units to protect the integrity of the vessels and avoid a potentially hazardous
situation
5.4.3. Material Selection
Corrosion resistance is not the only factor determining the choice of construction
materials. Other factors such as mechanical properties, workability, and weld ability,
as well as economic considerations such as price, availability, and delivery time, also
deserve attention. Stainless steels that have found wide use are the austenitic grades
AISI 316L and 317 L. Like all Cr-containing stainless steels, AISI 316L and 317 L
are not resistant to the action of sulfides. Hence it is imperative in plants using the
316L and 317 L grades in combination with CO2 derived from sulfur-containing gas,
to purify this gas or the CO2 thoroughly. In stripping processes, the process
conditions in the high-pressure stripper are most severe with respect to corrosion.
In the Stamicarbon CO2-stripping process, a higher-alloyed, but still fully austenitic
stainless steel (25 Cr 22 Ni 2 Mo) was chosen as construction material for the stripper
tubes. This choice ensures better corrosion resistance than 316L or 317L types of
material but still maintains the advantages of workability, weld ability, reparability,
and the cheaper price of stainless steel-type materials.
In the Snamprogetti stripping processes, titanium usually is chosen for this critical
application, although mechanically bonded bimetallic 25 Cr 22 Ni 2 Mo zirconium
tubes have also been suggested to improve corrosion resistance
In the ACES process, duplex alloys (ferrite austenitic) are used as construction
material for the stripper tubes.
5.4.4. Side Reactions
Three side reactions are of special importance in the design of urea production processes:
1. Hydrolysis of urea
CO(NH2)2 +H2ONH2COONH42NH3 +CO2 (3)
2. Biuret formation from urea:
2 CO(NH2)2NH2CONHCONH2 +NH3
(4)
(5)
All three side reactions have in common the decomposition of urea; thus, the extent to
which they occur must be minimized.
The hydrolysis reaction (3) is nothing but the reverse of urea formation. Whereas
this reaction approaches equilibrium in the reactor, in all downstream sections of
the plant the NH3 and CO2 concentrations in urea-containing solutions are such
22
that Reaction (3) is shifted to the right. The extent to which the reaction occurs is
determined by temperature (high temperatures favor hydrolysis) and reaction
kinetics; in practice, this means that retention times of urea-containing solutions at
high temperatures must be minimized.
The biuret reaction (4) also approaches equilibrium in the urea reactor the high
NH3 concentration in the reactor shifts Reaction (4) to the left, such that only a
small amount of biuret is formed in the reactor. In downstream section of the
plant, NH3 is removed from the urea solutions, thereby creating a driving force for
biuret formation. The extent to which biuret is formed is determined by reaction
kinetics; therefore, the practical measures to minimize biuret formation are the
same as described above for the hydrolysis reaction.
The iso-cyanic acid reaction (5) is also favored by low NH3 concentrations. This
reaction is especially relevant in the evaporation section of the plant. Here, low
pressures are applied, resulting in a transfer of NH 3 and HNCO into the gas phase
and, consequently, low concentrations of these constituents in the liquid phase.
Together with the relatively high temperatures in the evaporators, this shifts
Reaction (5) to the right. The extent to which this reaction occurs is again
determined by kinetics. The HNCO removed via the gas in the evaporators
collects in the process condensate from the vacuum condensers, where low
temperatures shift Reaction (5) to the left, again forming urea. As a result of this
mechanism of chemical entrainment, attempts to minimize entrainment from
evaporators with physical (liquid gas) separation devices are destined to be
unsuccessful.
23
24
Fig 16 Stamicarbon CO2-stripping urea process (The process suitable for combination with a granulation plant is
shown here; combination with prilling is also possible.)
a) CO2 compressor; b) Hydrogen removal reactor; c) Urea reactor; d) High-pressure stripper; e) Highpressure carbamate condenser; f) High-pressure scrubber; g) Low-pressure absorber; h) Low-pressure
decomposer and rectifier; i) Pre-evaporator; j) Low-pressure carbamate condenser; k) Evaporator; l) Vacuum
condensation section; m) Process condensate treatment CW= Cooling water; TCW= Tempered cooling water
Condensation of ammonia and carbon dioxide gases, leaving the stripper, occurs in the
high pressure carbamate condenser (e) at synthesis pressure. As a result, the heat
liberated from ammonium carbamate formation is at a high temperature. This heat is used
for the production of 4.5-bar steam for use in the urea plant itself. The condensation in
the high pressure carbamate condenser is not effected completely. Remaining gases are
condensed in the reactor and provide the heat required for the dehydration of carbamate,
as well as for heating the mixture to its equilibrium temperature. In an improvement to
this process, the condensation of off-gas from the stripper is carried out in a pre-reactor,
where sufficient residence time for the liquid phase is provided. As a result of urea and
water formation in the condensing zone, the condensation temperature is increased, thus
enabling the production of steam at a higher pressure level. The feed carbon dioxide,
invariably originating from an associated ammonia plant, always contains hydrogen. To
avoid the formation of explosive hydrogen oxygen mixtures in the tail gas of the plant,
hydrogen is catalytically removed from the carbon dioxide feed (b). Apart from the air
required for this purpose, additional air is supplied to the fresh carbon dioxide input
stream. This extra portion of oxygen is needed to maintain a corrosion-resistant layer on
the stainless steel in the synthesis section. Before the inert gases, mainly oxygen and
nitrogen, are purged from the synthesis section, they are washed with carbamate solution
from the low pressure recirculation stage in the high-pressure scrubber (f) to obtain a low
ammonia concentration in the subsequently purged gas. Further washing of the off-gas is
performed in a low pressure absorber (g) to obtain a purge gas that is practically
ammonia free. Only one low-pressure recirculation stage is required due to the low
ammonia and carbon dioxide concentrations in the stripped urea solution. Because of the
ideal ratio between ammonia and carbon dioxide in the recovered gases in this section,
water dilution of the resultant ammonium carbamate is at a minimum despite the low
25
pressure (about 4 bars). As a result of the efficiency of the stripper, the quantities of
ammonium carbamate for recycle to the synthesis section are also minimized, and no
separate ammonia recycle is required. The urea solution coming from the recirculation
stage contains about 75 wt% urea. This solution is concentrated in the evaporation section
(k). If the process is combined with a prilling tower for final product shaping, the final
moisture content of urea from the evaporation section is ca. 0.25 wt %. If the process is
combined with a granulation unit, the final moisture content may vary from 1 to 5 wt %,
depending on granulation requirements. Higher moisture contents can be realized in a
single-stage evaporator, whereas low moisture contents are economically achieved in a
two-stage evaporation section. When urea with an extremely low biuret content is
required (at a maximum of 0.3 wt %), pure urea crystals are produced in a crystallization
section. These crystals are separated from the mother liquor by a combination of sieve
bends and centrifuges and are melted prior to final shaping in a prilling tower or
granulation unit. The process condensate emanating from water evaporation from the
evaporation or crystallization sections contains ammonia and urea. Before this process
condensate is purged, urea is hydrolyzed into ammonia and carbon dioxide (l), which are
stripped off with steam and returned to urea synthesis via the recirculation section. This
process condensate treatment section can produce water with high purity, thus
transforming this wastewater treatment into the production unit of a valuable process
condensate, suitable for, e.g., cooling tower or boiler feed water makeup. Since the
introduction of the Stamicarbon CO2-stripping process, some 125 units have been built
according to this process all over the world.
5.5.2.2. Snamprogetti Ammonia-and Self-Stripping Processes
In the first generation of NH3 and self strip ping processes, ammonia was used as
stripping agent. Because of the extreme solubility of ammonia in the urea containing
synthesis fluid, the stripper effluent contained rather large amounts of dissolved
ammonia, causing ammonia overload in downstream section of the plant. Later versions
of the process abandoned the idea of using ammonia as stripping agent; stripping was
achieved only by supply of heat .Even without using ammonia as a stripping agent, the
NH3:CO2ratio in the stripper effluent is relatively high. So the recirculation section of the
plant requires an ammonia-carbamate separation section the process uses a vertical layout
in the synthesis section. Recycle within the synthesis section, from the stripper via the
high pressure carbamate condenser, through the carbamate separator back to the reactor,
is maintained by using an ammonia-driven liquid-liquid ejector. In the reactor, which is
operated at 150 bars, NH3:CO2molar feed ratio of 3.5 is applied .The stripper is of the
falling film type? Since stripping is achieved thermally, relatively high temperatures
(200-2100C) are required to obtain a reasonable stripping efficiency. Because of this high
temperature, stainless steel is not suitable as a construction material for the stripper from
a corrosion point of view; titanium and bimetallic zirconium stainless steel tubes have
been used Off gas from the stripper is condensed in a kettle type boiler. At the tube side
of this condenser the off gas is absorbed in recycled liquid carbamate from the medium
pressure recovery section. The heat of absorption is removed through the tubes, which are
cooled by the production of low pressure steam at the shell side. The steam produced is
used effectively in the back end of the process .In the medium pressure decomposition
and recirculation section, typically operated at 18 bar, the urea solution from the high
26
27
carbamate condenser; q) Low-pressure carbamate receiver; r) Low-pressure off-gas scrubber; s) First evaporation
heater; t) First evaporation separator; u) Second evaporation heater; v) Second evaporation separator; w) Wastewater
treatment; x) Vacuum condensation section
CW= Cooling water.
flow. The urea solution from the stripper, with a typical NH3 content of 12 wt %, is
purified further in the subsequent medium- and low-pressure decomposers (i, j),
operating at 19 and 3 bar, respectively. Ammonia and carbon dioxide separated from the
urea solution here are recovered through stepwise absorption in the low- and mediumpressure absorbers (h, k). Condensation heat in the medium-pressure absorber is
transferred directly to the aqueous urea solution feed in the final concentration section. In
this final concentration section (l), the purified urea solution is concentrated further either
by two-stage evaporation up to 99.7% for urea prills production or by a single
evaporation up to 98.5% for urea granule production. Water vapor formed in the final
concentrating section is condensed in surface condensers (q) to form process condensate.
Part of this condensate is used as an absorbent in the recovery sections, whereas the
remainder is purified in the process condensate treatment section by hydrolysis and steam
stripping, before being discharged from the urea plant. The highly concentrated urea
solution is finally processed either through the prilling tower (o) or via the urea
granulator (p). Instead of concentration via evaporation, the ACES process can also be
combined with a crystallization section to produce urea with low biuret content. Until
now, the ACES process has been used in seven urea plants.
29
30
31
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6. Environmental Aspects
The benefits of using a nitrogenous fertilizers is obvious because the crops grow taller,
and are healthier therefore yielding a higher crop and therefore cheaper, more plentiful
food.
There are always disadvantages. If after applying the fertilizer and it rained or when
too much fertilizer is used it gets into the streams or rivers and pollutes them. In the
rivers, the fertilizer does the same as it would on land, the river plants grow and algae
grow rapidly because of the abundant food supply. The algae then die in large numbers.
The bacteria feeding on the dead plant material use up the oxygen in the water, Fish may
then die because of the lack of oxygen in the water. Also too high of nitrates in the
drinking water is a health hazard, particularly with infants. Nitrates can interfere with the
oxygen flow in the blood stream.
33
34
enclosed or have a cover over the uppermost screen. Emissions are ducted from
the process for recovery or reuse.
Bagging and bulk loading operations are also a source of particulate emissions.
Dust is emitted from each type of bagging process during final filling when dust
laden air is displaced from the bag by the ammonium nitrate. The potential for
emissions during bagging is greater for coated than for uncoated material. It is
expected that emissions from bagging operations are primarily the kaolin, talc or
diatomaceous earth coating matter. About 90 percent of solid ammonium nitrate
produced domestically is bulk loaded. While particulate emissions from bulk
loading are not generally controlled, visible emissions are within typical state
regulatory requirements (below 20 percent opacity).
The total of mass emissions per unit is usually lower for feed grade prilling production
than for agricultural grade prills, due to lower airflows. Uncontrolled particulate emission
rates for fluidized bed prilling towers are higher than those for non-fluidized bed prilling
towers making agricultural grade prills, and are approximately equal to those for nonfluidized bed feed grade prills.
35
Ambient air conditions can affect prilling tower emissions. Available data indicate that
colder temperatures promote the formation of smaller particles in the prilling tower
exhaust. Since smaller particles are more difficult to remove, the efficiency of prilling
tower control devices tends to decrease with ambient temperatures. This can lead to
higher emission levels for prilling towers operated during cold weather. Ambient
humidity can also affect prilling tower emissions. Air flow rates must be increased with
high humidity, and higher air flow rates usually cause higher emissions. In the solids
screening process, dust is generated by abrasion of urea particles and the vibration of the
screening mechanisms. Therefore, almost all screening operations used in the urea
manufacturing industry are enclosed or are covered over the uppermost screen. Emissions
attributable to coating include entrained clay dust from loading, in-plant transfer, and
leaks from the seals of the coater.
6.2.2 Effluents; Wastewater;
Wastewater from the fertilizer industry can be classified into four groups:
36
ammonia if gases are not recovered in a closed loop so that no aqueous ammonia
emissions occur.
6.2.2.3 Nitric Acid Production
Nitric acid production generates relatively little wastewater since there is no process
wastewater source. Steam condensate generated in nitrogenous fertilizer processing is
characterized by dissolved and suspended solids, alkalinity, and hardness. The ammonia
vaporizer blow-down should have the ammonia vaporized and recovered into the process.
The waste oil should be reprocessed.
6.2.2.4 Ammonium Nitrate Production
Wastewater effluent is discharged from cooling tower blow down, backwash from
multi-media filters and from equipment and floor washing. Loss of ammonium nitrate to
drain from a large number of sources is a potential problem for all ammonium nitrate
plants. Causes are different kinds of leaks and washings.
Ammonium nitrate manufacturing produces process wastewater in the neutralization
process, the evaporation unit, and air cooling equipment. The vacuum condenser in
ammonium nitrate plants is a source of wastewater. Most scrubbing operations are also a
source of wastewater. The steam condensate leaving the neutralizer can be purified.
Purification can be achieved by stripping, distillation and membrane separation processes
as reverse osmosis. Ion exchange can also be considered but there are some safety
concerns which must be addressed. The steam can be used in the evaporator or to preheat
and evaporate ammonia and to preheat nitric acid. The solution from wet scrubbers is
normally recycled.
6.2.3 Solid Wastes:
For all fertilizers plants, solid materials may be found in storage piles, settled dust and
other similar forms. The following are the major solid wastes in different production lines
of fertilizers.
6.2.3.1 For Nitrogenous Fertilizers
Ammonia Production;
Solid wastes are generated due to the usage of many catalysts types and
quantities. The spent catalysts cannot be purified or recycled, hence, they create a
disposal problem which should be checked. These catalysts are considered
hazardous, due to their heavy metals content (chromium and nickel). Another
solid waste problem is the filling material for absorption tower. They are
consumed and disposed off-site.
37
Catalysts used in the steam reforming process need to be replaced every two to six
years. Spent catalysts contain oxides of hexa valent chromium, zinc, iron, and
nickel. They are typically returned to the manufacturer or other metal recovery
companies for recycling and reclamation of valuable materials.
Urea Production
Prills coating material in the bagging section are collected and recycled.
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7. Economic Aspects
7.1 Economic Analysis:
Costs of production estimates for different urea processes in different parts of the world
should be carried out.
The major contributor to the urea cost is the cost of ammonia. Since all the urea plants are
situated next to ammonia facilities, the effect of transferring ammonia into the urea
process at cash cost and full cost should be examined. Additionally, a cost of production
estimate for the production of urea based on market price ammonia should be done.
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8. Quality Specifications
8.1 Urea Quality Specifications:
8.1.1 Prilled Urea:
1- White prilled
2- Mass part nitrogen: 46.2%
3- Biuret, not more than: 1.0%
4- Moisture not more than: 0.5%
5- Granule size: 1mm to 4mm 90% min.
6- Free ammonia: 160 ppm max.
7- Melting point: 32o C
8- Physical properties:
Non radioactive
White
Free flowing
Free from harmful substances
100% treated against caking
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B
Higher Grade First Grade
98
No standard
No standard
34.4
No standard
34.4
0.2
0.2
0.2
0.3
0.3
0.3
5.0
4.0
5.0
4.0
5.0
4.0
0.2
No standard
No standard
93
No standard
No standard
No standard
95
95
No standard
80
50
0.0
0.0
0.0
5(0.5)
7(0.7)
10(1.0)
8(0.8)
100
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100
100
9. References
Ullmann`s encyclopedia, encyclopedia of industrial chemistry.
Kent and Riegel's handbook, industrial chemistry and biotechnology.
Encyclopedia of chemical processing, volume 1, 2006.
http://www.agriservices.com/pdf/uan.pdf (Cited in October 2011)
http://www.chemsystems.com (Cited in October 2011)
http://www.valetimegroup.com (Cited in October 2011)
http://www.agrodev.com (Cited in October 2011)
http://www.efma.org/Product-Stewardship
programe10/images/EFMABATURE.pdf (Cited in October 2011)
9. http://www.cyberax.eu/book/657680/urea-final-report (Cited in October 2011)
10. http://www.stamicarbon.com/UAN.html (Cited in October 2011)
1.
2.
3.
4.
5.
6.
7.
8.
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