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Ammonium Nitrate. Broadly defined, fertilizer ammonium nitrates include straight ammonium nitrate (AN), containing
3334% N, ammonium sulfate nitrate (ASN) 26% N, and calcium ammonium nitrate [39368-85-9] (CAN) 2026% N. Worldwide,
the estimated total production of these materials is about one-half straight AN. Most of the balance is CAN. The ASN and CAN
grades are used primarily because of greater safety and better storage and handling qualities. Ammonium nitrate fertilizers were
produced and used to some extent in Europe prior to 1942, but became of importance only after World War II when plants that had
been producing ammonium nitrate for munitions were converted to fertilizer production. Ammonium nitrate rapidly became the
leading solid nitrogen fertilizer both in the United States and worldwide, and held that position until about 1975, at which time its use
was equalled and then surpassed by that of synthetic urea. Figure 6 gives world consumption of N fertilizers from 1955 through
1990. For the year ended June 30, 1990, world consumption of ammonium nitrate in solid form was 26:4 £ 106 t (8:86 £ 106 t N ) or
about 11% of total world consumption of fertilizer nitrogen (9). United States consumption data for the same period (Fig. 3) show
that only 7% of U.S. nitrogen consumption was furnished as solid ammonium nitrate, although an additional 20% was furnished as
ureaammonium nitrate solutions.

Fig. 6. World trends in types of nitrogenous fertilizers consumed, where (| ) represents anhydrous ammonia, ammonium
phosphates, cogranulated mixtures, fluid mixtures; ({ { { ), urea, including that in nitrogen solutions; (¢ ¢ ¢ ¢), ammonium nitrate,
including that in nitrogen solutions; ({ ¢ { ), ammonium sulfate; and ({ ¢ ¢ { ) others.

In the United States, only high grade (3334% N) ammonium nitrate is produced, and, because of the oxidizing nature and
explosive potential of this material, strict handling precautions are required (10) (see EXPLOSIVES AND PROPELLANTS, EXPLOSIVES).
Several other countries, France, Russia, Romania, and the UK also allow production of the high grade product, whereas others, for
safety reasons, allow only the CAN grades (2026% N). Ammonium nitrate fertilizers are highly regarded because of the rapid
agronomic response, especially true in the cooler latitudes. For assimilation by the roots of most plants (rice is an exception), all
fertilizer nitrogen must first be converted in the soil to nitrate form (11,12). For non-nitrate fertilizers in the cooler areas, this process
may be rather slow. Ammonium nitrate is produced from ammonia and nitric acid (qv). The acid also is produced from anydrous
ammonia (see AMMONIUM COMPOUNDS).
Prilling and Granulation. Ammonium nitrate is normally produced initially in the form of a 75 to 85% solution
saturated at 40 to 77C. Conversion to solid prills or granules suitable for fertilizer use requires high temperature concentration of
the solution to 96 99 + % ammonium nitrate content followed by solidification from that solution by cooling and drying in either a
prilling tower or a granulation system.
The usual prilling operation and the design of prilling towers have been described in detail (13). Basically, a highly concentrated
solution of ammonium nitrate is sprayed as small droplets into the top of a tall tower countercurrent to an updraft of cool air.
Solidification occurs in the form of small spheres (prills), usually of 1 to 3 mm particle diameter. A relatively short tower, typically
about 21 to 30 m in height, and a feed of 99.599.8% solution is used to produce high density prills. The prill hardness and particle
size are about optimum under those conditions. If there is proper control of solution concentration and air flow, no further drying is
required. When lower (96 to 99%) solution concentrations are used, a taller tower is required, but the prills are of lower density, and
passage through a heated dryer often is required.
Treatment of prilling tower effluent air to avoid atmospheric pollution is a particularly difficult problem. Partly for this reason,
granulation has, to some extent, been introduced as an alternative to prilling. Another advantage of granulation is greater particle-size

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flexibility, which assumes importance when producing closely sized product for use in bulk blending. The Spherodizer granulation
process developed by Cominco Ltd. (Canada) and C & I/Girdler, Inc. (14,15) is one of the more advanced granulation processes.
Very concentrated ammonium nitrate solution is sprayed onto a rolling bed of solid particles in a rotating drum, resulting in the
formation of granules by layering and solidification. The granules contain only 0.10.5% moisture and require no further drying.
From a screening operation, oversize granules are crushed and recycled to the granulator along with undersize particles to serve as
nuclei for forming more product-size granules. The product size is controlled by choice of screen size. Air pollution (qv) is virtually
eliminated by wet scrubbing in a manner that is simple and economical compared to that required for a standard prilling operation.
The granules are harder than prills.
Pan granulation of ammonium nitrate also has been developed commercially (16,17). Essentially water-free melt
(<0:5%moisture ) is sprayed onto a cascading bed of fines (usually crushed recycle) in a tilted, rotating pan. Production of 1820 t/h
is common. Product made in this manner is said to require no conditioning. The pan is an excellent size classifier, making it easy to
produce granules of any desired size from 1 to 11 mm diameter. Advantages of pan granulation are ease of granule size control,
hardness of granule, and simplicity of pollution control.
Fire and Explosion Hazard. Ammonium nitrate is a strong oxidizing agent, and mixing it with certain materials,
including fertilizer potassium chloride, can induce self-heating and combustion. In addition, ammonium nitrate has the potential for
explosive decomposition under certain conditions of high temperature and pressure. Mixture of ammonium nitrate with small
amounts (even <1%) of carbonaceous material or certain other materials sensitizes ammonium nitrate to detonation. Serious fires
and explosions have occurred as a result of mishandling ammonium nitrate. The worst of the explosions was that at Texas City,
Texas in 1947 where two shiploads of ammonium nitrate fertilizer conditioned with petrolatum and paraffin wax exploded, killing
500 people and injuring 3000. Extensive studies of ammonium nitrate self-heating and detonation have since been carried out
(1820), and conditioning with organic materials no longer is allowed. As a result of extensive studies it has been concluded that
ammonium nitrate can be safely produced, stored, and handled if simple and reasonable precautions are taken. The thermal stability
of fertilizers containing ammonium nitrate has been evaluated and discussed at length (21), and a review of ammonium nitrate plant
safety measures has been published (22).
Conditioning. The production of low moisture (00.3%) granules or prills greatly reduces the likelihood of any caking
problems. However, in the absence of preventive measures, a volume change that accompanies a crystal transition at 32.3C causes
degradation of crystals, prills, and granules, which increases susceptibility to moisture absorption and caking. Additives (internal
conditioners) that have been used commercially to shift the transition temperature away from usual storage temperatures include
potassium nitrate, magnesium nitrate, and nucleating agents such as clay, talc, and other silicates. Coating dusts such as kieselguhr
(see DIATOMITE) and clays (qv) frequently are applied to ammonium nitrate prills as parting agents to reduce caking tendency. A
coating dosage of 1.5 to 2.0% is required for effectiveness, diluting product grades from 35 to about 33.5% N. Materials such as
petrolatum, paraffin waxes, and oils no longer are used as conditioners for ammonium nitrate, because of the effect on increasing
sensitivity to burning and explosion.
Packaging and Storage. Bags used for packaging ammonium nitrate must be impenetrable to water vapor because of
the hygroscopicity of the product which has a critical relative humidity of 59% at 30C. Simple paper, jute, or woven plastic bags are
unsatisfactory because their porosity allows rapid absorption of moisture, with resultant wetting and caking of the ammonium nitrate.
Suitable bags are of multiwall paper with a bitumen or polyethylene moisture-proofing layer. Monofilm bags of heavy (0.150.2 mm
thickness) polyethylene also are satisfactory. Jute or woven polypropylene bags with monofilm plastic liners are used in some
countries. In the United States, bags must carry precautionary labels indicating an oxidizing material. Any spilled material may
become contaminated and should not be rebagged. Bagged materials should not be stored within 76 cm of building walls or
partitions to allow for circulation of cooling air. Because pressure enhances caking, bagged material should not be stacked too high.
Ammonium nitrate should not be placed in storage while its temperature is above 54C. Higher temperatures accelerate caking.
Ammonium nitrate is extensively stored in bulk. It should be placed on a clean floor to avoid contamination. Ammonium
nitrate in bulk storage must be kept separate from other materials and not close to sources of heat. It is preferable to store the bulk
material in dehumidified areas but good quality granules and prills are often stored without dehumidification. Covering the floor and
pile with plastic sheet reduces moisture absorption and essentially eliminates caking. Material caked in storage should never be
dynamited or blasted. No smoking signs should be posted and observed, and all open flames should be kept away from the materials.
Transportation. Ammonium nitrate is safely transported by rail, road, and water. However, its transportation on U.S.
navigable waterways is restricted. Good ventilation must be provided and precautions taken against leakage and contamination. The
material must be completely isolated from other cargo and must be kept free of extraneous combustible materials.
Synthetic Urea. Urea (qv), CO(NH2)2, was first synthesized by Friedrich Wohler in 1828 by the reaction of ammonia and
cyanuric acid, both of which are inorganic starting materials (see CYANURIC AND ISOCYANURIC ACIDS). Prior to that synthesis, it was
generally believed that only living organisms could produce organic materials. In the 1990s, synthetic urea, albeit produced by a
different synthesis route, is the leading nitrogen fertilizer worldwide and the leading solid nitrogen fertilizer in the United States. For
the year ended June 30, 1991, world consumption of urea fertilizer in solid form (9) was 64:0 £ 106 t (29:4 £ 106 t N ). An additional
4:5 £ 106 t of urea (2:1 £ 106 t N ) was used in nitrogen solutions. In the United States, for the same period, consumption of solid
urea fertilizer was 4:6 £ 106 t (2:1 £ 106 t N ) and consumption of urea in nitrogen solutions was 2:2 £ 106 t (1:0 £ 106 t N ). Urea in
solid and solution form provided about 41% of total world fertilizer nitrogen and about 31% of total U.S. nitrogen.
Properties and Production. Several characteristics of urea make it particularly attractive as a fertilizer material. Its

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nitrogen content of 46.6% is considerably higher than that of ammonium nitrate (35.0%), ammonium sulfate (21.2%), and any other
solid nitrogen fertilizer. This is a great advantage in storage, handling and shipping. Also, urea presents no burning or explosion
hazard, which is a significant advantage over ammonium nitrate. Urea also is less hygroscopic than ammonium nitrate, having a
critical relative humidity of 73% at 30C as compared to 59% for ammonium nitrate. This lower hygroscopicity translates to better
storage and handling properties, especially in bulk. Urea is cheaper to produce than ammonium nitrate, per unit of nitrogen, largely
because the nitric acid intermediate is not required.
Agronomically, both advantages and disadvantages have been ascribed to urea. A principal agronomic advantage over
ammonium nitrate is in the fertilization of flooded rice. In the anaerobic conditions of a flooded paddy the nitrate radical of
ammonium nitrate is partially reduced to gaseous N2O or N2, which results in considerable volatilization loss of nitrogen. Urea, on
the other hand, supplies only ammonia nitrogen, which is easily retained in the flooded paddy. The roots of rice plants are uniquely
able to utilize the ammonia directly, whereas absorption by the roots of most crops requires that ammonia first be converted to
nitrate through a nitrification process in the soil (11,12). This advantage of urea in rice fertilization resulted in its early preference in
the Far Eastern markets. In other areas of the world, there has been some reluctance to accept urea because of certain perceived
problems. For most crops, other than rice, urea in the soil must first undergo hydrolysis to ammonia and then nitrification to nitrate
before it can be absorbed by plant roots. One problem is that in relatively cool climates these processes are slow; thus plants may be
slow to respond to urea fertilization. Another problem, more likely in warmer climates, is that ammonia formed in the soil hydrolysis
step may be lost as vapor. This problem is particularly likely when surface application is used, but can be avoided by incorporation of
the urea under the soil surface. Another problem that has been encountered with urea is phytotoxicity, the poisoning of seed by
contact with the ammonia released during urea hydrolysis in the soil. Placement of urea away from the seed is a solution to this
problem. In view of the growing popularity of urea, it appears that its favorable characteristics outweigh the extra care required in its
use.
Commercial urea generally contains a small amount of the compound biuret [108-15-0], NH2CONHCONH2. For fertilizer use
other than foliar application, biuret contents of about 1.5% or less are not harmful, and under usual production conditions it is not
difficult to avoid higher biuret levels. For most foliar application, however, the level should not exceed 0.1%, and special production
modifications are usually required to ensure such a low level.
The technology of urea production is highly advanced. The raw materials required are ammonia and carbon dioxide.
Invariably, urea plants are located adjacent to ammonia production facilities which conveniently furnish not only the ammonia but
also the carbon dioxide, because carbon dioxide is a by-product of synthesis gas production and purification. The ammonia and
carbon dioxide are fed to a high pressure (up to 30 MPa (300 atm)) reactor at temperatures of about 200C where ammonium
carbamate [111-78-0], CH6N2O2, urea, and water are formed.
2 NH 3 + CO 2 !
ÃNH 2 COONH 4 + heat

NH 2 COONH 4 + heat!
ÃNH 2 CONH 2 + H 2 O
The fundamental chemistry and engineering requirements of the process have been studied and are described elsewhere (23,24).
Because an excess of ammonia is fed to the reactor, and because the reactions are reversible, ammonia and carbon dioxide exit
the reactor along with the carbamate and urea. Several process variations have been developed to deal with the efficiency of the
conversion and with serious corrosion problems. The three main types of ammonia handling are once through, partial recycle, and
total recycle. Urea plants having capacity up to 1800 t/d are available. Most advances have dealt with reduction of energy
requirements in the total recycle process. The economics of urea production are most strongly influenced by the cost of the raw
material ammonia. When the ammonia cost is representative of production cost in a new plant it can amount to more than 50% of
urea cost.
Prilling and Granulation. Worldwide, prilling is the most widely used method of solidifying urea, but the use of
granulation is increasing rapidly. In prilling, molten urea that is almost anhydrous is forced through spray heads or spinner buckets at
the top of a tower to produce droplets that fall through a countercurrent stream of air in which they solidify to form prills. Urea
prilling requires taller towers than ammonium nitrate prilling in order to achieve comparable particle size. The height of towers
ranges from 21 to 52 m. The temperature and rate of flow of air also affect the size and quality of prills. Urea prilling is an
economical method for finishing, but the prills have low strength and are generally too small for use in blending with granular
materials such as diammonium phosphate. Also, the prilling operation is a serious polluter, the abatement of which is costly because
of the large volume of dust-laden air that must be treated. For these reasons there is a strong trend toward granulation of urea.
Granulation is now the leading method of finishing urea in the United States. The granulation process that is used in the
United States almost exclusively is the Spherodizer process (14,15). In this process, granules are formed by successive spraying and
drying (layering) of concentrated urea solution on recycled granules in a rotating drum. Special design of the drum and sprays,
together with control of air flow, results in hard granules of particle size favorable for blending and other use (Fig. 2c). A somewhat
similar process, known as curtain granulation, was developed by the Tennessee Valley Authority (TVA) (25) and was operated on an
experimental basis. The internal design of the TVA drum includes a sloping baffle that provides a falling curtain of urea, onto which
the concentrated urea solution is sprayed. In Europe, some urea is granulated by pan-granulation methods pioneered by Norsk
Hydro (16). The method is particularly suited for producing extra large granules 4 mm or greater in diameter, known as

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forestry-grade urea, which are preferred for aerial application to forests.

Conditioning. Notwithstanding the more favorable critical humidity of urea, as compared with that of ammonium nitrate,
unconditioned urea still exhibits a tendency to cake in storage. Causes for such caking include plasticity or softness of particles,
pressure in storage, temperature changes, and absorption of moisture. Coating of prills or granules with 1 or 2% of a finely ground
absorbent clay is an effective anticaking treatment and was used on prilled urea almost exclusively until about the mid-1960s. This
procedure, however, undesirably diluted the nitrogen content of the product from 46 to 45%. Internal conditioning, that is inclusion
of an anticaking agent in the urea melt before prilling or granulation, has supplanted coating. The agent used almost exclusively is
formaldehyde [50-00-0], CH2O, which is effective in dosage of only 0.2 to 0.5%. This amount of additive does not lower nitrogen
content below 46%. In addition to providing anticaking of the final product, formaldehyde improves the granulation process by
reducing dust formation. Action of the additive apparently is that of a crystal modifier and hardner. During a time period when
possible health hazards of formaldehyde were being questioned, an alternative internal conditioner, sodium lignosulfonate
[8061-51-6], was developed. This additive also is effective at very low dosage level and is considered to be a competitive conditioner
(26).
Nitrogen Solutions. In the year ended June 30, 1990, 20% of the fertilizer nitrogen used in the United States was applied
in the form of ureaammonium nitrate solutions (Fig. 3). This amount equals the proportion furnished by solid urea (prills and
granules). The solutions used are urea-ammonium nitrate-water mixtures designed to take advantage of the unusually high joint
solubility of urea and ammonium nitrate. Properties of typical solutions are given in Table 4. Solutions contain from 28 to 32%
nitrogen, and have salt-out temperatures of ¡18 to ¡ 2± C . For either ammonium nitrate or urea alone in solution, nitrogen content
higher than about 18% results in too high a salt-out temperature for practical use; thus the favorable effect of the eutectic solubility is
obvious. Nonpressurized storage and handling of these solutions is entirely satisfactory, and, because of the fairly high nitrogen
content, transportation costs from points of production are reasonable. Production costs per unit of nitrogen are usually lower than
for nitrogen solids because of the elimination of concentration and prilling or granulation steps. Farmer preference for these
solutions is usually based on the favorable price, ease of handling and application, and/or ease and effectiveness of pesticide
incorporation in the solution. Many preemergent herbicides are compatible with the nitrogen solutions; thus it is economical and
effective to combine early season fertilization with preemergent herbicide treatment. These nitrogen solutions are used both for
direct field application and as a nitrogen ingredient in fluid mixed fertilizers.

Table 4. Properties of Urea Ammonium Nitrate Nonpressure Solutions

Parameter Solution
grade, % N 28 30 32
composition, wt %
ammonium nitrate 40.1 42.2 43.3
urea 30.0 32.7 35.4
water 29.9 25.1 20.3
specific gravity at 15.6C 1.283 1.303 1.32
salt-out temperature, C ¡18 ¡10 ¡2

The usual manufacturing process for nitrogen solutions involves blending urea and ammonium nitrate solutions in a mixing
tank in either a batch or continuous manner. The feed solutions contain about 83% ammonium nitrate and 7285% urea. The plants
usually are part of a nitrogen fertilizer complex that makes both of the required ingredients. The ammonium nitrate solution is
withdrawn from the production line and combined in the desired ratio with the urea solution also taken directly from the production
line. Mixing, transfer, and storage constitute the process steps. Nitrogen solutions can, however, cause serious corrosion. Ammonium
thiocyanate, sodium arsenite, sulfonate OA5, or a trace of free ammonia are often incorporated in the solution as corrosion
inhibitors. Aluminum is one of the more resistant equipment materials

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