http://www.essentialchemicalindustry.org/chemicals/urea.

html

Urea

Urea (carbamide), readily produced from ammonia and carbon

dioxide, is a very important chemical in the agricultural and the polymer industries.

Uses of urea
Urea is the world's most commonly used nitrogen fertilizer and indeed more urea is
manufactured by mass than any other organic chemical. Containing 46% N, it is the most
concentrated nitrogen fertilizer, and is readily available as free-flowing prills (granules). It is
the cheapest form of nitrogen fertilizer to transport and it is also the least likely to 'cake'. It is
therefore favoured in developing countries.

Figure 1 This rice

paddy field in Thailand
has been treated with
urea, the nitrogen-
containing fertilizer
that is most used in
developing countries.
By kind permission of
Kim Dixon.

While over 90% of urea produced is used as a fertilizer, it has other uses, which include the
manufacture of the melamine, used in melamine-methanal resins. Urea itself also forms
important resins.

An increasingly important use of urea is in reducing air pollution from diesel engines in cars,
buses and lorries. Diesel engines run at high temperatures and nitrogen and oxygen, from the
air, are able to react together under these conditions to produce high concentrations of nitric
oxide. One way to remove this pollutant is to allow it to react with ammonia to form nitrogen.
However it is not possible to use ammonia directly as it is too volatile and is poisonous.
Instead a solution of urea in water is injected into the hot gases emerging from the engine in
the exhaust. Urea is thermally decomposed to ammonia and carbon dioxide. This is the
reverse of the process used to make urea:

Unlike ammonia, urea is safe and easy to handle.

The products, ammonia and carbon dioxide, together with the exhaust gases, are passed
immediately over a catalyst in the exhaust system. Ammonia reduces the oxides of nitrogen
(mainly nitric oxide), formed in the combustion processes, to nitrogen. The process is
complex but the overall reaction can be represented thus:

The system is known as Urea SCR (urea-based selective catalytic reduction) and can reduce
pollution by nitrogen oxides to almost zero.

Figure 2 Urea tanks are now

standard equipment for most
new diesel lorries, buses and
cars in many countries. The
urea is added to the exhaust
gases as a 32% aqueous
solution often known as
BlueTEC. In this photo, a
Mercedes bus is being filled
with BlueTEC solution (with
the blue nozzle to the lower
tank) and diesel (the upper
tank).
By kind permission of Daimler
AG.

Several catalysts have been used. One series is based on transition metal oxides (for example
those of vanadium and tungsten) on a carrier, titanium dioxide. Another series is based on
zeolites, in which some of the cations have been exchanged with a metal such copper.
Figure 3 A Mercedes-Benz E-Class E300 BlueTEC
Hybrid car. The diesel engine is combined with an
electric motor which allows for purely electric
driving even at high speeds which reduces the
amount of pollutants significantly compared to a
pure diesel engine. The amount of nitrogen oxides
emitted is further reduced by the use of BlueTEC
solution, which converts the oxides in the exhaust
to nitrogen and water vapour.
By kind permission of Daimler AG.

Figure 4 A line diagram of the car above

illustrating five key elements in the design of
the exhaust system.
1 The oxidation catalyst is used to remove
unwanted hydrocarbons, ensuring that they
are oxidised to carbon dioxide and water.
The catalyst is usually based on platinum or
palladium.
2 Known as an NOx catalytic convertor, it
contains aluminium oxide on whose surface,
platinum and barium oxide are present. It
traps the oxides of nitrogen. When the solid
is saturated with the oxides, unburnt
hydrocarbons are allowed to flow through,
converting much of the mixture to nitrogen,
carbon dioxide and water vapour.
3 A filter which traps particulates (small
pieces of carbon and other solids).
4 A tank containing the solution of urea.
5 The SCR-catalytic convertor which contains
another catalyst, for example an oxide of
vanadium (or tungsten) on titanium dioxide,
which allows the exhaust gases, still
containing some nitrogen oxides, to react
with ammonia formed from the urea
solution, to produce exhaust gases with only
traces of the oxides.
By kind permission of Daimler AG.

Annual production of urea1

World 164 million tonnes
China 62 million tonnes

India 23 million tonnes

Middle East 20 million tonnes

Rest of Asia 18 million tonnes

FSU 12 million tonnes

North America 9.5 million tonnes

Europe 9.5 million tonnes

It is expected that the global annual production will increase to over 200 million tonnes by
20182.

1. Potash Corporation, 2013

2. International Fertilizer Industry Association, 2014

Manufacture of urea
Ammonia reacts with carbon dioxide to produce urea. Urea is always manufactured close to
an ammonia plant (Figure 5).

Ammonia and carbon dioxide are heated together at 450 K and 200 atm pressure. First
ammonium carbamate is formed, which rapidly decomposes to form urea:
Figure 5 An aerial view of a large plant in Alberta, Canada, in which ammonia is synthesized
and then converted to urea.
By kind permission of Agrium Inc.

Much of the urea is prilled (Figure 6) and sold in that form.

Figure 6 These small

spheres of urea are known
as prills. The prills are
formed by spraying
molten urea down a tower
up which air is pumped.
They are slightly smaller
than urea sold as granules
and are particularly useful
when the fertilizer is being
applied by hand.
By kind permission of
Agrium Inc.

Date last amended: 26th January 2017

JENIS2 PUPUK

http://www.landscape-and-garden.com/GardenSoil/FertilizerTypes
Fertilizer Types
Soil amendments are made by adding fertilizer to the soil but there are different types of
fertilizers. There is bulky organic fertilizer, such as cow manure, bat guano, bone meal,
organic compost and green manure crops. And then there is also chemical fertilizer which is
also referred to as inorganic fertilizer and is made up with different formulations to suit a
variety of specified uses. Though many governments and agricultural departments go to great
lengths to increase the supply of organic fertilizers, such as bulky organic manures and
composting materials, there is just not enough of these fertilizers available to meet the
existing and future fertilizer needs. Compared to organic compost, chemical or inorganic
fertilizers also have the added advantage of being less bulky. Being less bulky makes
chemical fertilizer easier to transport, both overland and from the soil into the plants itself,
because they get to be available to the plant relatively quickly when incorporated as part of
the plant-food constituents. Chemical fertilizer usually comes in either granular or powder
form in bags and boxes, or in liquid formulations in bottles. The different types of chemical
fertilizers are usually classified according to the three principal elements, namely Nitrogen
(N), Phosphorous (P) and Potassium (K), and may, therefore, be included in more than one
group.

Organic and Inorganic Chemical Nitrogenous Fertilizer types

This type of fertilizer is divided into different groups according to the manner in which the
Nitrogen combines with other elements. These groups are:

 Sodium Nitrates,
 Ammonium Sulphate and ammonium salts,
 Chemical compounds that contains Nitrogen in amide form, and
 Animal and plant by products.

Sodium Nitrates

Sodium Nitrates are also known as Chilates or Chilean nitrate. The Nitrogen contained in
Sodium Nitrate is refined and amounts to 16%. This means that the Nitrogen is immediately
available to plants and as such is a valuable source of Nitrogen in a type of fertilizer. When
one makes a soil amendment using Sodium Nitrates as a type of fertilizer in the garden, it is
usually as a top- and side-dressing. Particularly when nursing young plants and garden
vegetables. In soil that is acidic Sodium Nitrate is quite useful as a type of fertilizer.
However, the excess use of Sodium Nitrate may cause deflocculation.

Ammonium Sulphate

This fertilizer type comes in a white crystalline salt form, containing 20 to 21% ammonia
cal nitrogen. It is easy to handle and it stores well under dry conditions. However, during the
rainy season, it sometimes, forms lumps. (TIP: When these lumps do occur you should grind
them down to a powered form before use.) Though this fertilizer type is soluble in water, its
nitrogen is not readily lost in drainage, because the ammonium ion is retained by the soil
particles. A note of caution: Ammonium sulphate may have an acid effect on garden soil.
Over time, the long-continued use of this type of fertilizer will increase soil acidity and thus
lower the yield. (TIP: It is advisable to use this fertilizer type together with bulky organic
manures to safeguard against the ill effects of continued application of ammonium sulphate.)

The application of Ammonium sulphate fertilizer can be done before sowing, at sowing time,
or even as a top-dressing to the growing crop. Do however take care NOT to apply it along
with, or too close to, the seed, because in concentrated form, it affects seed germination very
adversely.

Ammonium Nitrate

This fertilizer type also comes in white crystalline salts. Ammonium Nitrate salts contains 33
to 35% nitrogen, of which half is nitrate nitrogen and the other half in the ammonium form.
As part of the ammonium form, this type of fertilizer cannot be easily leached from the soil.
This fertilizer is quick-acting, but highly hygroscopic thus making it unfit for storage. (TIP:
Coagulation and Granulation of this fertilizer can be combated with a light coating of the
granules with oil.) On a note of caution: Ammonium Nitrate also has an acid effect on the
soil, in addition this type of fertilizer can be explosive under certain conditions, and, should
thus be handled with care.

'Nitro Chalk' is the trade name of a product formed by mixing ammonium nitrate with about
40% lime-stone or dolomite. This fertilizer is granulated, non-hazardous and less
hygroscopic. The lime content of this fertilizer type makes it useful for application to acidic
garden soils.

Ammonium Sulphate Nitrate

This fertilizer type is available as a mixture of ammonium nitrate and ammonium sulphate
and is recognizable as a white crystal or as dirty-white granules. This fertilizer contains 26%
nitrogen, three-fourths of it in the ammoniac form and the remainder (i.e. 6.5%) as nitrate
nitrogen. Ammonium Sulphate Nitrate is non-explosive, readily soluble in water and is very
quick-acting. Because this type of fertilizer keeps well, it is very useful for all crops. Though
it can also render garden soil acidic, the acidifying effects is only one-half of that of
ammonium sulphate on garden soil. Application of this fertilizer type can be done before
sowing, at sowing time or as a top-dressing, but it should not be applied along the seed.

Ammonium Chloride

This fertilizer type comes in a white crystalline compound, which contains a good physical
condition and 26% ammoniac nitrogen. In general, Ammonium Chloride is similar to
ammonium sulphate in action. (TIP: Do not use this type of fertilizer on crops such as
tomatoes because the chorine may harm your crop.)

Urea

This type of fertilizer usually is available to the public in a white, crystalline, organic form. It
is a highly concentrated nitrogenous fertilizer and fairly hygroscopic. This also means that
this fertilizer can be quite difficult to apply. Urea is also produced in granular or pellet forms
and is coated with a non-hygroscopic inert material. It is highly soluble in water and
therefore, subject to rapid leaching. It is, however, quick-acting and produces quick results.
When applied to the soil, its nitrogen is rapidly changed into ammonia. Similar to ammonium
nitrate, urea supplies nothing but nitrogen and the application of Urea as fertilizer can be
done at sowing time or as a top-dressing, but should not be allowed to come into contact with
the seed.

Ammonia

This fertilizer type is a gas that is made up of about 80% of nitrogen and comes in a liquid
form as well because under the right conditions regarding temperature and pressure,
Ammonia becomes liquid (anhydrous ammonia). Another form, 'aqueous ammonia', results
from the absorption of Ammonia gas into water, in which it is soluble. Ammonia is used as a
fertilizer in both these forms. The anhydrous liquid form of Ammonia can be applied by
introducing it into irrigation water, or directly into the soil from special containers. Not really
suitable for the home gardener as this renders the use of ammonia as a fertilizer very
expensive.

Organic Nitrogenous Fertilizers

Organic Nitrogenous fertilizer is the type of fertilizer that includes plant and animal by-
products. These by-products can be anything from oil cakes, to fish manure and even to
dried blood. The Nitrogen available in organic nitrogenous fertilizer types first has to be
converted before the plants can use it. This conversion occurs through bacterial action and is
thus a slow process. The upside of this situation is that the supply of available nitrogen lasts
so much longer AND the amounts of this type of fertilizer may contain small amounts of
organic stimulants that contain other minor elements that might also be needed by the plants
that are being fertilized. Furthermore, they may also small amounts of organic stimulants that
they may contain, or of some of the minor elements needed by plant. Oil-cakes contain not
only nitrogen but also some phosphoric and potash, besides a large quantity of organic
matter. This type of fertilizer is used in conjunction with quicker-acting chemical fertilizers.

Then there is also blood meal which contains 10 to 12% highly available Nitrogen as well as
1 to 2% Phosphoric acid. Blood meal, used in much the same way as oilcakes, makes for a
quick remedy and can effectively be used on all types of soil as a type of fertilizer.

Fish meal which can be dried fish, fish-meal or even powder is extracted in areas where fish
oil is extracted. The resulting residue is used as a fertilizer type. Obviously depending on the
type of fish used, the available Nitrogen can be between 5 and 8% and the Phosphoric
content can be from 4 to 6%. Fish meal also constitutes a fast-acting fertilizer type which is
suitable for most soil types and crops. (TIP: In powder form it is at its best.)

Organic and Inorganic Chemical Phosphate Fertilizer Types

The Phosphate fertilizers are categorized as natural phosphates, either treated or processed,
and also by products of phosphates and chemical phosphates.

Rock Phosphate

As a type of fertilizer, rock phosphate occurs as natural deposits in some countries. This
fertilizer type has its advantages and disadvantages. The advantage is that with adequate
rainfall this fertilizer results in a long growing period which can enhance crops. Powdered
phosphate fertilizer is an excellent remedy for soils that are acidic and has a phosphorous
deficiency and requires soil amendments.

However, the disadvantage is that although phosphate fertilizer such as rock phosphate
contains 25 to 35% phosphoric acid, the phosphorous is insoluble in water. It has to be
pulverized to be used as a type of fertilizer before rendering satisfactory results in garden soil.
Thus it is not surprising that Rock Phosphate is used to manufacture superphosphate which
makes the Phosphoric acid water soluble.

Superphosphate

Superphosphate is a fertilizer type that most gardeners are familiar with. As a fertilizer type
one can get superphosphate in three different grades, depending on the manufacturing
process. The following is a short description of the different superphosphate fertilizer grades:

 Single superphosphate containing 16 to 20% phosphoric acid;

 Dicalcium phosphate containing 35 to 38% phosphoric acid; and
 Triple superphosphate containing 44 to 49% phosphoric acid.

Triple superphosphate is used mostly in the manufacture of concentrated mixed fertilizer

types.

The greatest advantage to be had of using Superphosphate as a fertilizer is that the phosphoric
acid is fully water soluble, but when Superphosphate is applied to the soil, it is converted into
soluble phosphate. This is due to precipitation as calcium, iron or aluminum phosphate,
which is dependent on the soil type to which the fertilizer is added, be it alkaline or acidic
garden soil. All garden soil types can benefit from the application of Superphosphate as a
fertilizer. Used in conjunction with an organic fertilizer, it should be applied at sowing or
transplant time.

Slag

Basic slag is a by-product of steel mills and is used as a fertilizer to a lesser extent than
Superphosphate. Slag is an excellent fertilizer that can be used to amend soils that are acidic
because of its alkaline reaction. For slag application to be an effective fertilizer it has to be
pulverized first.

Bonemeal

Bonemeal as a fertilizer type needs no introduction. Bone-meal is used as a phosphate

fertilizer type and is available in two types: raw and steamed. The raw bone-meal contains
4% organic Nitrogen that is slow acting, and 20 to 25% phosphoric acid that is not soluble in
water. The steamed bone-meal on the other hand has all the fats, greases, nitrogen and glue-
making substances removed as a result of high pressure steaming. But it is more brittle and
can be ground into a powder form. In powder form this fertilizer is of great advantage to the
gardener in that the rate of availability of the phosphoric acid depends on its pulverization.
This fertilizer is particularly suitable as a soil amendment for acid soil and should be applied
either at sowing time or even a few days prior to sowing. (TIP: As a fertilizer type, bone-meal
is slow acting and should be incorporated into the soil and not as a top-dressing.)
Organic and Inorganic Chemical Potassium Fertilizer types

Chemical Potassium fertilizer should only be added when there is absolute certainty that there
is a Potassium deficiency in your garden soil. Potassium fertilizers also work well in sandy
garden soil that responds to their application. Crops such as chilies, potato and fruit trees all
benefit from this type of fertilizer since it improves the quality and appearance of the
produce. There are basically two different types of potassium fertilizers:

 Muriate of potash (Potassium chloride) and

 Sulphate of potash (Potassium sulphate).

Both muriate of potash and sulphate of potash are salts that make up part of the waters of the
oceans and inland seas as well as inland saline deposits.
Muriate Of Potash

Muriate of potash is a gray crystal type of fertilizer that consists of 50 to 60% potash. All
the potash in this fertilizer type is readily available to plants because it is highly soluble in
water. Even so, it does not leach away deep into the soil since the potash is absorbed on the
colloidal surfaces. (TIP: Apply muriate of potash at sowing time or prior to sowing.)

Sulphate Of Potash

Sulphate of potash is a fertilizer type manufactured when potassium chloride is treated with
magnesium sulphate. It dissolves readily in water and can be applied to the garden soil at
any time up to sowing. Some gardeners prefer using sulphate of potash over muriate of
potash.

Different Types of Fertilizers

The different types of fertilizers with all its specifications and cautions that should be kept in
mind should not detract us from the joys of gardening. Thus to make it easier on most
gardeners and since this website is dedicated to the home gardener and growing our own
gardens the following section is geared towards the home gardener.

The different types of chemical and organic fertilizers that are usually commercially available
in most countries can be categorized further into:

 Complete inorganic fertilizers: – these types of inorganic fertilizers contain all three major
macronutrients, Nitrogen (N), Phosphorous (P) and Potassium (K). On the containers you will
find that these macronutrients are depicted as a ratio, e.g. 2:3:2 (22). Complete inorganic
fertilizers are usually applied at a rate of 60g/m2 or roughly 4 tablespoons per square meter.
 Special purpose fertilizer: – these types of fertilizer are formulated especially to target
certain plants' requirements or certain soil deficiencies. Of the examples that come to mind
here are the Blue Hydrangea Food, and straight fertilizer that is made up of one particular
plant nutrient for example lawn fertilizer.
 Liquid fertilizers: – these types of fertilizer come in a variety of formulations and even
include organic fertilizer, complete fertilizer as well as special purpose fertilizer. Some
examples of liquid fertilizer are Nitrosol and African Violet Food.
  Slow-release fertilizer: – these types of fertilizer are formulated to release their nitrogen at
a steady pace. On the packs of this fertilizer that are available commercially it will usually be
depicted as 3:1:5 (SR) where the SR indicates slow-release.
 Fertilizer with insecticide: – these types of fertilizer that are prepared and combined with an
insecticide. One such example is Wonder 4:1:1 (21) + Karbaspray.

The reason why there are so many different types of chemical fertilizers in different
formulations is because different plants require different nutrients and different pH levels in
the soil. However, organic fertilizers have more diversity, and these types of fertilizers do not
burn plant roots, get into ground water, or affect surrounding growth as is the case when
using the different types of chemical fertilizer and NPK amendments.

https://en.wikipedia.org/wiki/Urea

Production[edit]
Urea is produced on an industrial scale: In 2012, worldwide production capacity was
approximately 184 million tonnes.[38]

Industrial methods[edit]
For use in industry, urea is produced from synthetic ammonia and carbon dioxide. As large
quantities of carbon dioxide are produced during the ammonia manufacturing process as a
byproduct from hydrocarbons (predominantly natural gas, less often petroleum derivatives), or
occasionally from coal, urea production plants are almost always located adjacent to the site
where the ammonia is manufactured. Although natural gas is both the most economical and the
most widely available ammonia plant feedstock, plants using it do not produce quite as much
carbon dioxide from the process as is needed to convert their entire ammonia output into urea. In
recent years new technologies such as the KM-CDR process[39][40] have been developed to
recover supplementary carbon dioxide from the combustion exhaust gases produced in the fired
reforming furnace of the ammonia synthesis gas plant, allowing operators of stand-alone nitrogen
fertilizer complexes to avoid the need to handle and market ammonia as a separate product and
also to reduce their greenhouse gas emissions to the atmosphere.
Synthesis[edit]

Urea plant using ammonium carbamate briquettes, Fixed Nitrogen Research Laboratory, ca. 1930

The basic process, developed in 1922, is also called the Bosch–Meiser urea process after its
discoverers. Various commercial urea processes are characterized by the conditions under
which urea forms and the way that unconverted reactants are further processed. The process
consists of two main equilibrium reactions, with incomplete conversion of the reactants. The first
is carbamate formation: the fast exothermic reaction of liquid ammonia with gaseous carbon
dioxide (CO2) at high temperature and pressure to form ammonium carbamate(H2N-COONH4):[41]
2 NH3 + CO2 ⇌ H2N-COONH4 (ΔH= -117kJ/mol at 110 atm and 160°C) [42]
The second is urea conversion: the slower endothermic decomposition of ammonium
carbamate into urea and water:
H2N-COONH4 ⇌ (NH2)2CO + H2O (ΔH= +15.5 kJ/mol at 160-180°C) [42]
The overall conversion of NH3 and CO2 to urea is exothermic,[6] the reaction heat from the
first reaction driving the second. Like all chemical equilibria, these reactions behave
according to Le Chatelier's principle, and the conditions that most favour carbamate
formation have an unfavourable effect on the urea conversion equilibrium. The process
conditions are, therefore, a compromise: the ill-effect on the first reaction of the high
temperature (around 190 °C) needed for the second is compensated for by conducting
the process under high pressure (140–175 bar), which favours the first reaction.
Although it is necessary to compress gaseous carbon dioxide to this pressure, the
ammonia is available from the ammonia plant in liquid form, which can be pumped into
the system much more economically. To allow the slow urea formation reaction time to
reach equilibrium a large reaction space is needed, so the synthesis reactor in a large
urea plant tends to be a massive pressure vessel.
Because the urea conversion is incomplete, the product must be separated from
unchanged ammonium carbamate. In early "straight-through" urea plants this was done
by letting down the system pressure to atmospheric to let the carbamate decompose
back to ammonia and carbon dioxide. Originally, because it was not economic to
recompress the ammonia and carbon dioxide for recycle, the ammonia at least would be
used for the manufacture of other products, for example ammonium nitrate or sulfate.
(The carbon dioxide was usually wasted.) Later process schemes made recycling
unused ammonia and carbon dioxide practical. This was accomplished by
depressurizing the reaction solution in stages (first to 18–25 bar and then to 2–5 bar)
and passing it at each stage through a steam-heated carbamate decomposer, then
recombining the resultant carbon dioxide and ammonia in a falling-film carbamate
condenser and pumping the carbamate solution into the previous stage.
The stripping concept[edit]
The "total recycle" concept has two main disadvantages. The first is the complexity of
the flow scheme and, consequently, the amount of process equipment needed. The
second is the amount of water recycled in the carbamate solution, which has an adverse
effect on the equilibrium in the urea conversion reaction and thus on overall plant
efficiency. The stripping concept, developed in the early 1960s by Stamicarbon in The
Netherlands, addressed both problems. It also improved heat recovery and reuse in the
process.
The position of the equilibrium in the carbamate formation/decomposition depends on
the product of the partial pressures of the reactants. In the total recycle processes,
carbamate decomposition is promoted by reducing the overall pressure, which reduces
the partial pressure of both ammonia and carbon dioxide. It is possible, however, to
achieve a similar effect without lowering the overall pressure—by suppressing the partial
pressure of just one of the reactants. Instead of feeding carbon dioxide gas directly to
the reactor with the ammonia, as in the total recycle process, the stripping process first
routes the carbon dioxide through a stripper (a carbamate decomposer that operates
under full system pressure and is configured to provide maximum gas-liquid contact).
This flushes out free ammonia, reducing its partial pressure over the liquid surface and
carrying it directly to a carbamate condenser (also under full system pressure). From
there, reconstituted ammonium carbamate liquor passes directly to the reactor. That
eliminates the medium-pressure stage of the total recycle process altogether.
The stripping concept was such a major advance that competitors such
as Snamprogetti—now Saipem—(Italy), the former Montedison (Italy), Toyo Engineering
Corporation (Japan), and Urea Casale (Switzerland) all developed versions of it. Today,
effectively all new urea plants use the principle, and many total recycle urea plants have
converted to a stripping process. No one has proposed a radical alternative to the
approach. The main thrust of technological development today, in response to industry
demands for ever larger individual plants, is directed at re-configuring and re-orientating
major items in the plant to reduce size and overall height of the plant, and at meeting
challenging environmental performance targets.[43][44]
Side reactions[edit]
It is fortunate that the urea conversion reaction is slow. If it were not it would go into
reverse in the stripper. As it is, succeeding stages of the process must be designed to
minimize residence times, at least until the temperature reduces to the point where the
reversion reaction is very slow.
Two reactions produce impurities. Biuret is formed when two molecules of urea combine
with the loss of a molecule of ammonia.
2 NH2CONH2 → H2NCONHCONH2 + NH3
Normally this reaction is suppressed in the synthesis reactor by maintaining an
excess of ammonia, but after the stripper, it occurs until the temperature is reduced.
Biuret is undesirable in fertilizer urea because it is toxic to crop plants, although to
what extent depends on the nature of the crop and the method of application of the
urea.[45] (Biuret is actually welcome in urea when is used as a cattle feed
supplement).
Isocyanic acid results from the thermal decomposition of ammonium cyanate,
which is in chemical equilibrium with urea:
NH2CONH2 → NH4NCO → HNCO + NH3
This reaction is at its worst when the urea solution is heated at low pressure,
which happens when the solution is concentrated for prilling or granulation (see
below). The reaction products mostly volatilize into the overhead vapours, and
recombine when these condense to form urea again, which contaminates the
process condensate.
Corrosion[edit]
Ammonium carbamate solutions are notoriously corrosive to metallic
construction materials, even more resistant forms of stainless steel—especially
in the hottest parts of the plant such as the stripper. Historically corrosion has
been minimized (although not eliminated) by continuous injection of a small
amount of oxygen (as air) into the plant to establish and maintain a passive
oxide layer on exposed stainless steel surfaces. Because the carbon dioxide
feed is recovered from ammonia synthesis gas, it contains traces of hydrogen
that can mingle with passivation air to form an explosive mixture if allowed to
accumulate.
In the mid 1990s two duplex (ferritic-austenitic) stainless steels were introduced
(DP28W, jointly developed by Toyo Engineering and Sumitomo Metals
Industries[46] and Safurex, jointly developed by Stamicarbon and Sandvik
Materials Technology (Sweden).[47][48]) These let manufactures drastically reduce
the amount of passivation oxygen. In theory, they could operate with no oxygen.
Saipem now uses either zirconium stripper tubes, or bimetallic tubes with a
titanium body (cheaper but less erosion-resistant) and a metallurgically bonded
internal zirconium lining. These tubes are fabricated by ATI Wah Chang (USA)
using its Omegabond technique.[49]
Finishing[edit]
Urea can be produced as prills, granules, pellets, crystals, and solutions.
Solid forms[edit]
For its main use as a fertilizer urea is mostly marketed in solid form, either
as prills or granules. The advantage of prills is that, in general, they can be
produced more cheaply than granules and that the technique was firmly
established in industrial practice long before a satisfactory urea granulation
process was commercialized. However, on account of the limited size of
particles that can be produced with the desired degree of sphericity and their low
crushing and impact strength, the performance of prills during bulk storage,
handling and use is generally (with some exceptions[50]) considered inferior to
that of granules.
High-quality compound fertilizers containing nitrogen co-granulated with other
components such as phosphates have been produced routinely since the
beginnings of the modern fertilizer industry, but on account of the low melting
point and hygroscopic nature of urea it took courage to apply the same kind of
technology to granulate urea on its own.[51] But at the end of the 1970s three
companies began to develop fluidized-bed granulation. The first in the field was
Nederlandse Stikstof Maatschappij, which later became part of Hydro Agri
(now Yara International).[52] Yara eventually sold this technology to Uhde GmbH,
whose Uhde Fertilizer Technology (UFT) subsidiary now markets it. Around the
same time Toyo Engineering Corporation developed its spouted-bed process,
comprising a fluidized bed deliberately agitated to produce turbulent
ebullation.[53] Stamicarbon also undertook development work on its own fluidized-
bed granulation system, using film sprays rather than atomizing sprays to
introduce the urea melt, but shelved it until the 1990s, when there was for a time
considerable doubt about the commercial future of the Hydro (UFT)
process.[54] As a result, the Stamicarbon technology is now commercialized and
highly successful. More recently, Urea Casale introduced a different fluidized-
bed granulation system: the urea is sprayed in laterally from the side walls of the
granulator instead of from the bottom. This organizes the bed into two cylindrical
masses contrarotating on parallel longitudinal axes. The raw product is uniform
enough not to require screens.[55]
Surprisingly, perhaps, considering the product particles are not spherical,
pastillation using a Rotoform steel-belt pastillator is gaining ground as a urea
particle-forming process as a result of development work by Stamicarbon in
collaboration with Sandvik Process Systems (Germany). Single-machine
capacity is limited to 175 t/d, but the machines are simple and need little
maintenance, specific power consumption is much lower than for granulation,
and the product is very uniform. The robustness of the product appears to make
up for its non-spherical shape.[56][57]