Chapter 21

Fertilizers

1. INTRODUCTION
Besides the three basic elements of carbon, hydrogen, and oxygen that
are common to all plants, there are 16 other elements known to be essential
to good plant growth. Their percentages are given below.

95% basic elements44% C, 6% H, 45% O

3.5% primary nutrients2.0% N, 0.5% P, 1.0% K
1.3% secondary nutrientsCa, Mg, S
0.1% micronutrientsB, Cl, Cu, Fe, Mn, Mo, Zn (Co, F, I in animals
also)

This chapter is concerned with the three primary nutrients making up

most fertilizers: nitrogen, phosphorus, and potassium. The usual sources of
nitrogen are ammonia, ammonium nitrate, urea, and ammonium sulfate.
Phosphorus is obtained from phosphoric acid or phosphate rock. Potassium
chloride is mined or obtained from brine and the sulfate is mined in small
amounts. Potassium nitrate is made synthetically. These chemicals have
already been described under inorganic chemicals of the top 50. Sources for
the three primary nutrients are given in Fig. 21.1.
 Nitrogen Phosphorus Potassium

Air, hydrocarbons, or Sulfur Potash* x

.;
Raw materials hydrogen Phosphate rock

Primary Nitric Phosphoric SuI fun c

nutrient chemicals Ammonia * acid acids acid

Derived Ammonium I , Triple Normal

Ammonium Nitric Ammonium ',-super- v super-
nutrient chemicals Urea nitrate* j phosphate phosphate >
sulfaU* phosphate * phosphate

Mixers
Bulk blenders of dry
granular materials Liquid blenders
n Lmmoniaior-
ranulators
Dry mixers
of powder materials

Retailers Dealers

Farmers and commercial users

Consumers

* Major direct application materials sold through blender-retailers or dealers.

Figure 21.1 Major fertilizer materials. (Source: Kline & Company, Inc.)
 Phosphatic Pert.
Nitrogenous Pert.
Mixed Fertilizers
Billions of Dollars

Year

Figure 21.2 U.S. shipments of fertilizers. (Source: Annual Survey of Manufactures)

Nitrogen
Phosphate
Potash
Billions of Pounds

Year

Figure 21.3 U.S. production of fertilizers. (Source: Chemical Economics Handbook

and UN Food and Agriculture Organization)
2. HISTORY AND ECONOMICS OF FERTILIZERS
Although the modern era of fertilizers began with the work of Justus von
Liebig in 1840 and the first U.S. patent for a mixed fertilizer was granted in
1849, the use of large amounts of synthetic fertilizers was popularized only
after World War II. Fertilizer consumption increased eight times between
1950 and 1980 worldwide. U.S. shipments of fertilizers is summarized in
Fig. 21.2. Phosphatic Fertilizers (NAICS 325312) had a very fast increase
from $1 billion in the early 1970s to $4.4 billion in 1980. Since then it has
increased only slowly to $5.5 billion. Nitrogenous fertilizers (NAICS
325311) have also had a similar trend to 1980 and have dropped recently to
that level now. Mixed Fertilizers (NAICS 325314) have had a more constant
increase in the last few years. Fig. 21.3 gives trends in nitrogen, phosphate,
and potash fertilizer production. Nitrogen and phosphorus production in
billions of pounds have increased slowly through the years except for a few
drops in the 1980s. Potash production is always much less and has been
steady or decreasing in the last 25 years. Table 21.1 shows the uses of
fertilizers on various types of crops. Note that nearly half of all fertilizers is
used on one crop: corn. Wheat, hay, soybeans, and cotton consume most of
the rest of fertilizers used on crops.

3. FERTILIZERMATERIALS

Fertilizers may contain all three primary nutrients, in which case they are
called mixed fertilizers, or they may contain only one active ingredient,
called direct application fertilizers. Recently the ratio of direct application to
mixed fertilizers is 60:40 in the U.S. Nitrogen and potash are consumed
mainly from direct application fertilizers. Phosphate is applied mostly from
mixed fertilizers.
Table 21.1 Uses of Fertilizers on Crops

Corn 44%
Wheat 17
Hay 9
Soybeans 6
Pasture and range 5
Cotton 3
Other crops 10
Other feed grains 6
Source: Chemical Economics Handbook
 Table 21.2 Percentage of Direct Application Fertilizers

Nitrogen solutions 24%

Anhydrous and aqueous ammonia 22
Potassium chloride 20
Ammonium nitrate 10
Urea 8
Superphosphates 5
Ammonium sulfate 3
Ammonium phosphate 2
Miscellaneous 6

3.1 Direct Application Fertilizers

Table 21.2 lists all important direct application materials and their
percentage of direct application fertilizers. Direct application use is
increasing mainly because of anhydrous ammonia gas becoming popular. It
can be pumped in 3-6 in. beneath the soil during plowing and is absorbed by
the soil rapidly. Nitrogen solutions can also be applied in this manner
(mixture of free ammonia, ammonium nitrate, urea, and water).

3.2 Mixed Fertilizers

The primary advantage of mixed fertilizers is that they contain all three
primary nutrientsnitrogen, phosphorus, and potassiumand require a
smaller number of applications. They can be liquids or solids. The overall
percentage of the three nutrients must always be stated on the container. The
grade designation is %N-%P2O5-%K2O. It is commonly called the NPK
value. Note that it is an elemental percentage only in the case of nitrogen.
Phosphorus and potassium are expressed as oxides. Thus an NPK value of
6-24-12 means that 6% by weight is elemental nitrogen, 24% is phosphorus
pentoxide, and 12% is potash. One way of remembering the order is that
they are alphabetical according to the English name (mtrogen, phosphorus,
potassium). A changeover to a grade designation by the three elemental
bases is being resisted by the industry.
3.2.1 Nitrogen Sources

The nitrogenous chemicals ammonia, urea, ammonium nitrate, and

ammonium sulfate are used as sources of nitrogen in mixed fertilizers. A
mixture is also quite popular and is relatively cheap, since the mixed
nitrogen solution from which pure urea is made can be used as fertilizer.
Nitrogen solutions have their own code number. An example would be
414(19-66-6), meaning 41.4% total nitrogen, 19% free ammonia, 66%
ammonium nitrate, and 6% urea with the rest being water. Over 100
nitrogen solutions are marketed. Although the solutions are cheap, the solids
do not have a vapor pressure problem and are more easily transported. The
present breakdown of nitrogen fertilizer production is ammonia, 40%;
nitrogen solutions, 30%; urea, 14%; ammonium nitrate, 8%; and ammonium
sulfate, 8%.

3.2.2 Phosphorus Sources

All phosphorus fertilizers come from wet process phosphoric acid or

directly from phosphate rock. Normal superphosphate, triple or concentrated
superphosphate, and ammonium phosphate are the three common types used.
Normal or ordinary superphosphate (NSP or OSP) is mostly monocalcium
phosphate and calcium sulfate. It is made from phosphate rock and sulfuric
acid and is equated to a 20% P2O5 content. It led the market until 1964. The
production of normal superphosphate is similar to that for the manufacture of
wet process phosphoric acid (Chapter 2, Section 3) except that there is only
partial neutralization. Normal superphosphate is no longer used to any great
extent. The following reaction is one example of an equation that represents
this process.

CaF2-3Ca3(PO4)2 + 17H2O + 7H2SO4 ^

3[CaH4(PO4)2-H2O] + 2HF + 7(CaSO4 2H2O)

normal superphosphate (NSP)

Triple superphosphate (TSP), made from phosphate rock and phosphoric

acid, is mostly mono- and dicalcium phosphate. It is equivalent to a 48%
P2O5 content. It led the market from 1965-1967.

CaF2-3Ca3(P04)2 + 14H3PO4 ^ 10CaH4(PO4)2 + 2HF

triple superphosphate (TSP)
 The ammonium phosphates took over the lead in 1967. Diammonium
phosphate (DAP) is made from wet process phosphoric acid of about 40%
P2O5 content and ammonia. The usual finishing NH3:H3PO4 mole ratio is
1.85-1.94:1. Monoammonium phosphate (MAP) is made with a final
NH3)H3PO4 ratio of 1:1. Current production percentages for phosphate
fertilizers are DAP, 67%; MAP, 26%; and TSP, 7%.

2NH3 + H3PO4 ^ (NH4)2HP04

(DAP)

NH3 + H3PO4 > NH4H2PO4

(MAP)

3.2.3 Potassium Sources

Most potassium in fertilizers is the simple chloride salt, having a 60-62%

K2O equivalent. Certain crops such as potatoes and tobacco do not like high
amounts of chloride. For these crops KNO3, K2SO4, or K2Mg(SO4)2 may be
used. Florida citrus crops need magnesium nutrients so K2Mg(SO4)2 is
favored there.

3.2.4 Ammoniation

When an ammonia fertilizer is mixed with a superphosphate there is a

chemical reaction that occurs, changing the active ingredient's structure. The
following equations illustrate this chemistry.

(1) H3PO4 + NH3 ** NH4H2PO4

(2) Ca(H2PO4)2 -H2O + NH3 ** CaHPO4 + NH4H2PO4 + H2O

(3) NH4H2PO4 + NH3 ^ (NH4)2HPO4

(4) 2CaHPO4 + CaSO4 + 2NH3 ^Ca(PO4)2 + (NH4)2SO4

(5) NH4H2PO4 + CaSO4 H- NH3 ^ CaHPO4 + (NH4)2SO4

Reactions (1) and (2) are common for both normal and triple
superphosphate. Reaction (3) is important in triple superphosphate because
of the lack of large amounts of calcium sulfate. Reaction (5) is important
 Table 21.3 Advantages of Fertilizers

Liquids
Lower capital investment by the company
Less labor, handling, and conditioning
costs
More uniform composition
More uniform distribution on land
Solids
Less corrosion of equipment
Better economics of costs of storing
smaller volumes
Solubility restrictions are not present
No crystallization problems in cold
weather

with normal superphosphate because of the large surplus of calcium sulfate

in this formulation.

4. LIQUIDS VS. SOLIDS

There are many different types of liquid and solid fertilizers but we give
only some generalizations about advantages of each. Liquid fertilizers are a
clear solution, a suspension of a solid in a liquid (aided by a suspending
agent), or a simple slurry of a solid in a liquid. Solid fertilizers contain no
liquid. Table 21.3 summarizes the advantages of liquids and solids.
Mixed solid fertilizers can be made by either direct granulation methods
(40%) or bulk blending (40%). Bulk blending is made by mechanical
mixing of the separate granular intermediate materials. It is usually done in
small plants near the point of use. This technique is employed because the
fertilizer can be "tailor-made" to fit the exact requirements of the user. Fluid
or liquid fertilizers (clear, suspension, and slurry) account for 20% of all
NPK mixed fertilizers.

5. CONTROLLED-RELEASE FERTILIZERS
Much recent research has centered on developing long-lasting slow-
release fertilizers to make application requirements less often. Urea-
formaldehyde resins in nitrogen fertilizers tie up the nitrogen for a longer
time, since degradation of the polymer occurs slowly by sunlight. This type
of fertilizer is especially popular for the high nitrogen content of home lawn
fertilizers. Sulfiir-coated urea (SCU) is also becoming a popular slow-
release nitrogen formulation. syw-Tetrahydrotriazone, made by reacting
urea, formaldehyde, and ammonia, can be added to urea fertilizers.
 syw-tetrahydrotriazone

Triazones form ammonium ions much more slowly than urea. Slow-
release potassium is also being developed. A coating of sulfur seems to
delay its release. For phosphorus Mg(NH4)PO4 is becoming popular because
it has a slower dissolution rate in the soil. Despite the simple chemicals used
in most fertilizers, some interesting research and formulation work will keep
chemists involved in the industry for some time to come.

Suggested Readings

Kent, Riegel's Handbook of Industrial Chemistry, pp. 367-407.