4/27/24, 5:08 PM Phosphate Rock Properties

Laboratory Testing Consulting & Engineering Process Equipment Contact Us

Menu

Phosphate Rock Properties

 Previous Next 

Three fundamental methods are employed in decomposing phosphate

Table of Contents
rock:

1. Reduction by carbon at high temperature.

2. Treatment with one or more acids.
3. Calcination or fusion with silica, sodium salts, magnesium minerals, or small quantities of
phosphoric acid.

The products derived from phosphate rock by these treatment methods may be divided into the
following live broad groups:

1. Elemental phosphorus.
2. Phosphoric acid.
3. Phosphatic fertilizers.
4. Phosphate salts.
5. Other phosphorus compounds.

Phosphorus and phosphoric acid have certain direct industrial applications, but they are more
commonly used as intermediates in manufacturing the products included in the other three
groups.

The various intermediate and end products derived from phosphate rock and their more
important industrial applications are shown in figure 1.

https://www.911metallurgist.com/properties-phosphate-rock/ 1/40
4/27/24, 5:08 PM Phosphate Rock Properties

https://www.911metallurgist.com/properties-phosphate-rock/ 2/40
4/27/24, 5:08 PM Phosphate Rock Properties

The earliest use of phosphatic materials was for fertilizer purposes, but fur many years these
materials were applied in a raw or natural state.

The dung of birds was employed by the Carthaginians before 200 B.C., and the early agricultural
writers recommended applications of natural phosphate materials to increase crop yields . The
Incas of Peru and the American Indians applied fish and guano to the soil long before America
was discovered by Europeans. Although the composition of such phosphate materials was
unknown, their function in increasing crop yields was generally recognized. In 1769 Gahn, a
Swedish chemist, reported that phosphorus was an essential constituent of bones, but the
untreated natural materials continued to be the main sources of fertilizer until about the middle of
the 19th century.

In 1840, Leibig suggested dissolving bones with sulfuric acid to render the contained phosphorus
soluble and available to crops. In 1857 he pointed out that phosphate rock could be treated in a
similar manner. This marked the beginning of a commercial fertilizer industry, which has grown to
enormous proportions and now includes many manufactured products derived from phosphate
rock.

Elemental phosphorus was first produced in 1669 by Brandt, a German chemist, who on treating
desiccated urine in a retort found that a vapor was evolved that burst into flame on contact with
air, forming dense, white fumes. He called this vapor phosphorus or “light bearer.” Later, it was
found that this vapor could be condensed to a yellow liquid (if protected from air) and collected
under water.

Elemental phosphorus was manufactured on a small scale by reducing acidulated bones or

phosphate rock with carbonaceous materials, but 200 years elapsed before Readman (1889)
patented the first practical electric furnace for making elemental phosphorus.

The commercial production of phosphorus in America was undertaken by the Oldbury

Electrochemical Co. in 1896, using a relatively small single-phase furnace with an annual capacity
of about 750 tons of phosphorus.

For many years the demand for phosphorus was small, but during World War I manufacturing
facilities were expanded rapidly to supply military requirements. After World War I the phosphorus
industry continued to grow, owing to improved processing and recovery methods and to
increased demand for high-quality phosphate products. Elemental phosphorus requirements
during World War II, coupled with the availability of relatively low cost, hydroelectric power,
caused further expansion. This industry now occupies a position of major importance.

https://www.911metallurgist.com/properties-phosphate-rock/ 3/40
4/27/24, 5:08 PM Phosphate Rock Properties

Elemental Phosphorus
Properties and Uses
White phosphorus is a highly poisonous white or lemon-colored waxlike solid having a melting
point of 44.1° C., a boiling point of 280° C., and a specific gravity of 1.82. It is nearly insoluble in
water, is slightly soluble in alcohol and certain other organic liquids, and dissolves readily in
carbon disulfide and in ammonia. At 34° C. white phosphorus ignites spontaneously in air,
evolving white fumes of phosphorus pentoxide (P2O5), which in turn combine with water to form
orthophosphoric acid (H3PO4).

Red phosphorus is a dark-red amorphous solid obtained by heating white phosphorus to 250° C.
out of contact with air. This variety has a specific gravity of 2.20 and a melting point of 590° C., is
nonpoisonous, and does not ignite until heated to a temperature of approximately 260° C. in air.
Red phosphorus is insoluble in water, carbon disulfide, and amnionia, but it is soluble in alkali
solutions.

Elemental phosphorus has few industrial applications. During World War II, however, large
tonnages were used in tracer bullets, incendiary bombs, and the production of smokescreens.

Poisonous pastes for exterminating rodents and household insect pests contain phosphorus, but
in recent years these have been largely supplanted by various organic compounds.

Substantial quantities of white phosphorus are added to molten metals, such as tin and copper, to
produce special alloys.

The main industrial application of red phosphorus is in the match industry. The striking surface of
safety-match packages consists of red phosphorus, powdered glass, and glue, which ignite the
head of a match drawn across the surface.

Most elemental phosphorus is converted to phosphoric acid for use in manufacturing numerous
industrial products.

Manufacture of Phosphorus
The early methods of manufacturing limited quantities of elemental phosphorus were crude,
cumbersome, and costly. Large tonnages are now produced in huge electric furnaces from raw
materials that are plentiful.

Phosphorus also has been successfully produced in blast furnaces similar to those used in pig-iron
manufacture, but in recent years the availability of relatively low-cost hydroelectric energy in some
Southern and Western States has resulted in the general adoption of the electric-furnace process

https://www.911metallurgist.com/properties-phosphate-rock/ 4/40
4/27/24, 5:08 PM Phosphate Rock Properties

for elemental-phosphorus manufacture. Figure 2 shows a modern electric-furnace plant for

making elemental phosphorus.

No matter which type of furnace is used, the fundamental principles involved are essentially the
same decomposition at high temperature of calcium phosphate in the presence of silica and
carbon to produce elemental phosphorus, carbon monoxide, and a molten silicate slag. The
overall reaction in its simplest form is represented by equation (1).

Ca3(PO4)2 + 3SiO2 + 5O = 3CaSiO3 + P2 + 5CO………………………………………..(1)

Raw Materials and Preparation of Furnace Charge

This raw materials that comprise a furnace charge are phosphate rock, silica, and carbon in the
form of coke breeze. They are so proportioned that there is ample carbon for reduction and
enough silica to combine with the lime in the phosphate rock to form a readily fusible slag.

When a high-grade phosphate rock is used, silica is added in the form of gravel, but in recent
years lower grade siliceous phosphates have been that obviate the necessity of adding substantial
https://www.911metallurgist.com/properties-phosphate-rock/ 5/40
4/27/24, 5:08 PM Phosphate Rock Properties

quantities of silica bubbles.

The furnace feed must be lumps or coarse granules to prevent bridging of the charge, insure
steady and uniform descent of the materials, and maintain an open texture that permits ready
evolution of phosphorus vapor and other volatile products without carrying over excessive
quantities of dust or finely divided unreacted material into the auxiliary equipment. When finely
divided phosphate rock is used, it is briquetted, sintered, or nodulized to the proper size. The
methods of preparing various types of furnace charges and their relative advantages are discussed
in a comprehensive engineering report by the Tennessee Valley Authority (TVA). Table 1 shows a
typical burden for a phosphorus electric furnace using relatively high grade rock and the final
composition of the charge.

Operating Steps

https://www.911metallurgist.com/properties-phosphate-rock/ 6/40
4/27/24, 5:08 PM Phosphate Rock Properties

The carefully proportioned mixture of phosphate rock, silica, and coke breeze is fed continuously
into the furnace and distributed in uniform layers around the carbon electrodes. As decomposition
of the charge proceeds, a molten slag (relatively free from phosphorus) and a small quantity of
ferro-phosphorus collect in the bottom of the furnace crucible and are drained off periodically
through tap holes.

The volatile products, consisting of approximately 90 percent carbon monoxide, 7 percent

phosphorus, and about 3 percent other gaseous products, led through a refractory-lined steel
pipe into the Cottrell precipitators (maintained at a temperature well above the dewpoint of
phosphorus), when the fine dust carried over by the furnace gases is collected.

From the hot precipitators the mixture of gases and phosphorus vapor enters the condensing
system where it is sprayed with water and the bulk of the phosphorus condensed. The process
water and elemental phosphorus drain into a sump, and the phosphorus forms a heavy liquid
layer protected from oxidation by the overlying water. The process water, which is recirculated, is
maintained at a temperature slightly above the melting point of phosphorus. A small part of the
phosphorus is oxidized in the water, and soda ash is added intermittently to neutralize the dilute
acid solution. The washed gases are then drawn through a vacuum pump, which removes the
remaining phosphorus. From the vacuum pump the cleaned gas, consisting almost entirely of
carbon monoxide, either passes to a storage tank or is utilized directly as a fuel. Figure 3 shows a
flowsheet of an integrated plant for manufacturing both phosphorus and phosphoric acid.

https://www.911metallurgist.com/properties-phosphate-rock/ 7/40
4/27/24, 5:08 PM Phosphate Rock Properties

Phosphorus Recovery and Cost

Under average operating conditions, 90.5 percent of the phosphorus in the charge is volatilized,
6.5 percent is contained in the ferrophosphorus produced, and 3.0 percent remains in the slag. Of
the phosphorus volatilized, 97 percent (nearly 88 percent of that in the furnace charge) is
recovered.

The power consumption per ton of recovered phosphorus ranges from 12,000 to 13,000 kw.-hr.,
depending on the nature of the charge and the efficiency of operation. The estimated cost of
producing elemental phosphorus in a plant comprising two 12,500-kw. furnaces producing 17,200
short tons of elemental phosphorus per year, as given by the TVA, is shown in table 2.

https://www.911metallurgist.com/properties-phosphate-rock/ 8/40
4/27/24, 5:08 PM Phosphate Rock Properties

Byproducts
The byproducts from making phosphorus by the electric-furnace process are ferrophosphorus (an
iron alloy containing about 23 percent of phosphorus), carbon monoxide gas, and a calcium
silicate slag.

There is a limited market for ferrophosphorus in manufacturing special types of steel. The carbon
monoxide gas is utilized as a supplementary fuel in preparing the phosphate charge for furnace
treatment. The furnace slag may be crushed and sized for railroad ballast, ground finely and used
as agricultural lining material, or converted into a lightweight concrete aggregate by treating the
molten material with steam as it is tapped from the furnace. Although much of the fluorine in the
furnace charge remains in the slag, a small percentage is volatilized and collected in the
phosphorus condensing water as fluosllicic acid. To minimize corrosion of the condensing
equipment, soda ash added to neutralize the acidity of the water. Vanadium is a potential
byproduct that may be recovered in smelting western phosphate rock, but the vanadium content

https://www.911metallurgist.com/properties-phosphate-rock/ 9/40
4/27/24, 5:08 PM Phosphate Rock Properties

of the phosphate rock in Florida and Tennessee is too low to warrant recovery. Fluorine, uranium,
chromium, and selenium also are possible byproducts of the elemental-phosphorus Industry.

Domestic Production
Table 3 gives the manufacturers of elemental phosphorus in the United States and the number
and location of phosphorus plants. The total estimated capacity of these plants, as well as the
actual annual production figures for 1930-57, are shown in table 4.

Virtually all manufacturers of phosphorus convert a large part of their output into phosphoric acid.

https://www.911metallurgist.com/properties-phosphate-rock/ 10/40
4/27/24, 5:08 PM Phosphate Rock Properties

Phosphoric Acid
Orthophosphoric acid (H3PO4), usually referred to as phosphoric acid, is not only the most
important acid of phosphorus but to some extent has displaced sulfuric acid in numerous
Industrial applications. Although sulfuric acid is the cheapest and most widely used commercial
acid, the sulfate radical (SO4) of the salts derived therefrom has little commercial value compared
with that of the phosphate radical (PO4) of salts produced from phosphoric acid.

Phosphoric acid is produced by two methods:

1. Oxidation of elemental phosphorus and hydration of the resultant P2O5.

2. Decomposition of phosphate rock with sulfuric acid and filtration of the phosphoric acid
from the insoluble residue.

Large tonnages of phosphoric acid are manufactured by both of these processes. Host of the acid
derived from elemental phosphorus is used in manufacturing relatively pure phosphate products;
the bulk of that produced by the sulfuric acid process is used in manufacturing phosphatic
fertilizers.

Properties of Phosphate Rocks

Anhydrous phosphoric acid forms prismatic crystals, which readily deliquesce in the air. As
ordinarily prepared, concentrated phosphoric acid is a clear, colorless, syrupy liquid (specific
gravity, 1.83), which attacks most metals and bases, forming the corresponding phosphate salts.
When heated to over 210° C., phosphoric acid loses part of its water of crystallization and is
converted to pyrophosphoric acid (H4P2O7). On heating above 400° C more water is driven off,

https://www.911metallurgist.com/properties-phosphate-rock/ 11/40
4/27/24, 5:08 PM Phosphate Rock Properties

and the pyrophosphoric acid is converted to metaphosphoric acid (HPO3). The successive
reactions are shown in equations (2) and (3).

2H3PO4 + heat = H4P2O7 + H2O……………………………………..(2)

H4P2O7 + heat = 2HPO3 + H2O……………………………………….(3)

Although phosphoric acid is used principally as an intermediate in manufacturing phosphate

compounds, it has many direct uses. Substantial tonnages are added directly to irrigating water
for fertilizer use and to ensilage and prepared stockfeeds to improve their nutrient qualities.
Appreciable tonnages of chemical-grade phosphoric acid are used instead of citric and tartaric
acids to impart tartness and palatability to soft drinks, jams, and jellies and as a defecating agent
in refining sugar. Smaller quantities are used in the synthesis of certain dyes, in the manufacture of
special types of glass, and as an ingredient of dental cement. In recent years phosphoric acid has
proved an effective catalyst, promoting certain chemical reactions when absorbed on a porous
medium such as diatomaceous earth. Substantial quantities of less pure acid are consumed in
pickling metals and depositing rust-resisting coatings thereon.

Pyrophosphoric and metaphosphoric acids are little used in the free or uncombined state, but
their salts (pyrophosphates and metaphosphates) have considerable commercial importance. The
polymetaphosphates are used in fertilizers, detergents, lubricants, and drilling muds.

Manufacture of Phosphoric Acid From Elemental

Phosphorus
The conversion of elemental phosphorus to phosphoric acid is effected in two stages: The
phosphorus is first oxidized to P2O5, which is then reacted with water to form the acid, according
to equations (4) and (5).

P4 + 5O2 = 2P2O5…………………………………………………………..(4)

P2O5 + 3H2O = 2H3PO4………………………………………………….(5)

Liquid phosphorus is pumped through a steam-jacketed pipeline to a water-cooled burner set

into the top of a cylindrical combustion chamber. There it is mixed with an excess of air and
oxidized at temperatures above 1,800° F. The domelike steel top of the combustion chamber is
lined with acid-resisting refractory material. The walls and bottom arc constructed of graphite
blocks set in asphalt cement. The combustion chamber is supported above ground level, and the
bottom is laid in a stainless-steel pan 5 inches deep to collect any acid that may seep through the
graphite blocks. To prevent oxidation of the graphite, the outside walls of the combustion
chamber art cooled by a curtain of water, which is deflected near the base of the chamber to
prevent it from entering any cracks in the chamber bottom.

https://www.911metallurgist.com/properties-phosphate-rock/ 12/40
4/27/24, 5:08 PM Phosphate Rock Properties

The P2O5 and gaseous products are fed through an opening near the bottom of the combustion
chamber into a graphite-lined cooler, where their temperature is reduced to about 350° F. They
then enter a steel cylindrical hydrator lined with acidproof brick, where they are sprayed with
water and the bulk of the P2O5 is converted to phosphoric acid. The cooled gases, containing
suspended particles of acid, then enter a Cottrell electrical precipitator where the remainder of the
acid is collected. The spent gase are discharged to the atmosphere through a tall stack.

Phosphoric acid of any desired concentration can be obtained by this process, but. it is customary
to produce acid containing 75 to 85 percent H3PO4.

Estimated Cost of Production

Table 5 gives the estimated cost of producing phosphoric acid from elemental phosphorus.

Manufacture of Phosphoric Acid by the Wet Process

Before extensive development of the electric-furnace process for making elemental phosphorus,
the bulk of the phosphoric acid consumed for industrial, uses was manufactured by treating
phosphate rock with sulfuric acid. This so-called “wet process” is still the main method utilized in
producing phosphoric acid for fertilizer use, but it has been largely displaced by the electric-
furnace process for high-grade chemicals and food products requiring relatively pure
concentrated phosphoric acid.

https://www.911metallurgist.com/properties-phosphate-rock/ 13/40
4/27/24, 5:08 PM Phosphate Rock Properties

The raw materials used in manufacturing phosphoric acid by the wet process consist of a medium-
grade phosphate rock (usually 30 to 32 percent P2O5) and sulfuric acid. The main reaction is that
between sulfuric acid and fluorapatite, producing phosphoric acid, calcium sulfate dihydrate
(gypsum), and volatile fluorine compounds. The main reactions in their simplest form are shown in
equation (6).

3Ca3(PO4)2·CaF2 + 10H2SO4 + 20H2O = 6H3PO4 + 2HF + 10(CaSO4·2H2O)…………..(6)

Actually the hydrofluoric acid is not evolved but reacts instantaneously with silica to form
hydrofluosilicic acid, which is decomposed so that gaseous silicon tetrafluoride is liberated. As
virtually all phosphate rock contains appreciable calcium carbonate and iron and aluminum
compounds, more sulfuric acid must be added to decompose these impurities.

Modern plants for manufacturing phosphoric acid by the wet process are designed for continuous
operation. A typical process is described as follows: Calculated quantities of concentrated sulfuric
acid (60° to 66° B.) diluted with weak phosphoric acid and a recirculated slurry of partly
decomposed phosphate rock are fed continuously to one or more agitator tanks, then discharged
into the first of a series of mixing tanks to which weighed quantities of finely ground phosphate

https://www.911metallurgist.com/properties-phosphate-rock/ 14/40
4/27/24, 5:08 PM Phosphate Rock Properties

rock (90 percent minus-100-mesh) are continuously added. Mechanical stirrers mix these
ingredients, and compressed air is introduced to cool the slurry. The gases evolved are treated
with water to move the fluorine compounds. Complete decomposition of the rock and extraction
of P2O5 is effected by a countercurrent system. The resultant phosphoric acid is separated from
precipitated gypsum and other insoluble constituents by washing the slurry on vacuum filters. The
phosphoric acid from the first filter (30 to 32 percent H3PO4) is termed “production acid.” This
acid is concentrated by evaporation to 70 to 75 percent H3PO4 before it is used for making
fertilizers. If the acid is to be used for high-quality phosphate products, certain purification steps
are required. Under carefully controlled conditions the recovery of phosphoric acid in a well-
operated plant ranges from 94 to 96 percent.

Figure 4 shows a flowsheet of the wet process for manufacturing phosphoric acid and the
production of fertilizer therefrom.

Byproducts
The major byproducts that may be recovered in manufacturing phosphoric acid by the wet
process are: Calcium sulfate, fluorine compounds, vanadium, and uranium. Chronium and
selenium also have been reported in certain phosphate rocks.

Gypsum
Over 1 ton of gypsum is produced for each ton of phosphate rock consumed in making
phosphoric acid. However, this gypsum is diluted with various impurities (chiefly silica and
silicates) which detract from its value. It has been used to a limited extent in the manufacture of
precast blocks for interior partitions of buildings, but no phosphoric-acid plants were utilizing this
byproduct in 1957.

https://www.911metallurgist.com/properties-phosphate-rock/ 15/40
4/27/24, 5:08 PM Phosphate Rock Properties

Fluorine Products
All commercial phosphate rock except that of recent origin contains 3 to 4 percent fluorine. When
the rock is treated with sulfuric acid, a large part of this fluorine is evolved as silicon tetrafluoride
https://www.911metallurgist.com/properties-phosphate-rock/ 16/40
4/27/24, 5:08 PM Phosphate Rock Properties

(SiF4), which reacts with water to form fluosilicic acid and gelatinous silica. The fluosilicic acid may
be filtered, concentrated, and marketed as such, or it may be converted into the fluosilicates of
sodium, potassium, ammonium, or magnesium. Substantial quantities of sodium fluosilicate are
converted into sodium fluoride. Fluosilicates have many industrial applications, including ceramics
and insecticides. The advent of water fluoridation may greatly increase the demand for fluosilicic
acid, as it is estimated that full fluoridation of domestic water supplies would require 23,000 tons
of fluorine in the form of fluosilic, acid or its compounds.

Vanadium
Some phosphate rock contains a small quantity of vanadium oxide (V2O5). The phosphate
deposits of the Western States, for instance, contain 0.07 to 0.40 percent vanadium as compounds
soluble in sulfuric acid. A process for recovering vanadium from phosphate rock in marketable
form has been successfully developed and used, but the operation was discontinued in 1955.
Processing uranium ore yields more than enough vanadium to supply the present domestic
demand.

Uranium
The Florida pebble-phosphate deposits and deposits in the Western States contain about 0.015
percent U3O8. When phosphoric acid is produced by the wet process, the uranium is dissolved
and may be recovered by reduction of the acid solution and treatment with organic liquids that
selectively extract the uranium compounds. The organic mixture is separated from the acid
solution by centrifuging, and the uranium Is precipitated as a fluoride. The uranium precipitate
then is purified and the organic solution recirculated.

In 1957 approximately 3.1 million tons of domestic phosphate rock was used to manufacture
phosphoric acid by the wet process in the United States. If the average uranium oxide content is
assumed to be 0.015 percent, the total U3O8 in this rock was 468 short tons.

Estimated Cost of Production

Table 6 gives the quantities of phosphate rock and sulfuric acid required and the estimated cost of
manufacturing phosphoric acid by the wet process, using Florida pebble-phosphate and sulfuric
acid derived from elemental sulfur.

Domestic Production of Phosphoric Acid

Table 7 gives the annual production of phosphoric acid (50 percent H3PO4) in the United States,
1941-57.

https://www.911metallurgist.com/properties-phosphate-rock/ 17/40
4/27/24, 5:08 PM Phosphate Rock Properties

The manufacture of phosphoric acid from elemental phosphorus and by the wet process
expanded from 696,570 short tons in 1944 to 4,332,090 short tons in 1957, an increase of more
than 3.6 million short tons or over 400 percent. Except for 1947 and 1949, the quantity of acid
produced by the wet process exceeded that derived from elemental phosphorus.

https://www.911metallurgist.com/properties-phosphate-rock/ 18/40
4/27/24, 5:08 PM Phosphate Rock Properties

https://www.911metallurgist.com/properties-phosphate-rock/ 19/40
4/27/24, 5:08 PM Phosphate Rock Properties

https://www.911metallurgist.com/properties-phosphate-rock/ 20/40
4/27/24, 5:08 PM Phosphate Rock Properties

Phosphatic Fertilizers
Although industrial uses for products derived from phosphate rock have expanded greatly during
the past 25 years, the bulk of the phosphate rock produced was, and probably will continue to be,
consumed largely for fertilizers. Phosphate fertilizers include a wide variety of products. Some are
applied to the soil mainly for their phosphate value, whereas others consist of simple or double
salts so mixed that they contain two or more of the main plant-nutrient elements (N, P, and K) in
definite proportions. Within the past 25 years there has been an increasing trend toward the use
of more concentrated fertilizer materials to offset increased manufacturing and transportation
costs.

Figure 5 shows the composition of certain phosphate products containing one, two, or all three of
the major plant-food nutrients.

Fertilizers derived from phosphate rock may be grouped conveniently in the following major
categories:

1. Water-soluble phosphates.
2. Citrate-soluble or available phosphates.
3. Citrate-insoluble phosphates.

The agricultural availability of phosphate products is considered as the sum of the contained
water-soluble and citrate-soluble P2O5.

Water-Soluble Phosphates
Water-soluble phosphates comprise a number of highly soluble products. These products include
ordinary (normal) superphosphate, concentrated superphosphate, ammonium phosphates,
potassium phosphates, double salts of ammonium and potassium phosphates, and mixtures
containing soluble phosphates and nitrates.

Normal Superphosphate
Normal superphosphate is a relatively dry, porous product consisting essentially of a mixture of
monocalcium phosphate (a water-soluble phosphate salt) and calcium sulfate. Its available P2O5
content ranges from 18 to 22 percent, depending on the grade of rock and the free -moisture
content of the final product.

The process consists of mixing finely ground phosphate rock containing 32 percent or more P2O5
with sulfuric acid (55° B.) in the ratio of 100 parts of rock to 85 parts of acid. The resultant slurry is
stirred vigorously for several minutes and then discharged into a chamber or “den,” where the
chemical reactions continue and the product hardens into a porous cake. After a period of 1 to 24
hours the cake is removed (usually by mechanical means) and the product transferred to a storage

https://www.911metallurgist.com/properties-phosphate-rock/ 21/40
4/27/24, 5:08 PM Phosphate Rock Properties

pile, where the chemical reactions are completed (curing) within several weeks. The product is
then disintegrated, screened, and shipped (in bulk or bags) or mixed with potash and nitrogenous
compounds to make complete fertilizers.

As nearly all phosphate rock contains different proportions of acid-consuming impurities, the
chemical reactions involved are complex. The main reaction in making normal superphosphate is
shown in equation (7).

Ca3(PO4)2 + 2H2SO4 + H2O = CaH4(PO4)2·H2O + 2CaSO4……………………………….(7)

Hydrofluoric acid, formed from the fluorine in phosphate rock, reacts with the contained silica to
give silicon tetrafluoride (SiF4), which is evolved as a gas.

Host superphosphate plants are equipped with spray towers to absorb the silicon tetrafluoride,
which reacts with water to produce fluosilicic acid and gelatinous silica. Many plants utilize the
resulting solution to manufacture salts of fluosilicic acid.

Ordinary superphosphate requires no artificial drying and is the simplest phosphate fertilizer to
manufacture. Where low-cost sulfuric acid is available and hauls to the market are short,
superphosphate is usually the cheapest phosphate fertilizer to use. However, it is often more
economical to ship concentrated superphosphate, if the cost of transportation to consuming
centers is a major factor.

Concentrated Superphosphate
Concentrated superphosphate, as its name implies, is a product containing a higher percentage of
P2O5 than ordinary or normal superphosphate. As the production of concentrated
superphosphate entails the use of phosphoric acid, the plant is usually built adjacent to one that
manufactures phosphoric acid by the wet process.

Concentrated superphosphate ranges in grade from 25 to 48 percent available P2O5. The lower
grade is usually manufactured by decomposing phosphate rock with a mixture of sulfuric and
phosphoric acids; the higher grade (also called triple superphosphate) is produced by treating the
rock with phosphoric acid alone. Triple superphosphate contains little or no calcium sulfate.

The main reaction involved is shown in equation (8).

Ca3(PO4)2 + 4H3PO4 + 3H2O = 3CaH4(PO4)2·H2O……………………………(8)

No manufacture concentrated superphosphate using wet-process phosphoric acid, finely ground

phosphate rock (more than 31 percent P2O5) is intimately mixed with phosphoric acid. The
resultant slurry is discharged directly from the mixer onto a conveyor or directly into a reaction bin
where it hardens to a relatively stiff mass. The partly cured product is transferred to a pile where

https://www.911metallurgist.com/properties-phosphate-rock/ 22/40
4/27/24, 5:08 PM Phosphate Rock Properties

the chemical reactions are completed (curing). Then the material is ground, or dried and ground,
screened, and either shipped directly or mixed with potash and nitrogen compounds to make
complete fertilizers.

To make granulated concentrated superphosphate, the slurry of phosphoric acid and phosphate
rock is mixed with returned fines and crushed oversized material and put through a mixer and
drier. The granules are then sized, the oversize and undersize material returning to the circuit.

The production of ordinary superphosphate and concentrated superphosphate in the United

States, 1945-49 (average) and 1950-57, is shown in table 8.

Ammoniated Superphosphate
Both ordinary superphosphate and concentrated superphosphate contain some free acid, as well
as an acid salt (monocalcium phosphate) that can combine with substantial quantities of ammonia
without decreasing the availability of the contained P2O5.

Ammoniated superphosphate is produced by mixing calculated quantities of either ammonia gas

or a nitrogenous solution with the superphosphate in a rotating vessel. The free acid and part of
the acid salt CaH4(PO4)2 react with the ammonia to produce dicalcium phosphate (CaHPO4) and
one or more ammonium salts. The reactions in ordinary superphosphate containing sulfates are
shown in equation (9).

https://www.911metallurgist.com/properties-phosphate-rock/ 23/40
4/27/24, 5:08 PM Phosphate Rock Properties

CaH4(PO4)2·H2O + CaSO4 + 2NH3 = 2CaHPO4 + (NH4)2SO4 + H2O…………………………..(9)

When concentrated superphosphate containing little or no calcium sulfate is ammoniated, the

reaction is as shown in equation (10).

CaH4(PO4)2H2O + NH3 = CaHPO4 + (NH4)H2PO4 + H2O……………………………………..(10)

Little ammoniated superphosphate is manufactured and sold. It is produced chiefly as one

Ingredient resulting from the ammoniation of mixed fertilizers containing superphosphates.

Phosphate-Nitrate Fertilizers
Other phosphatic fertilizers containing water-soluble P2O5 include those obtained by treating
phosphate rock with nitric acid or with mixtures of nitric and other mineral acids. The substitution
of nitric for sulfuric acid as a reagent offers the advantage of producing mixtures containing two
main plant nutrient elements (N and P). On the other hand, all proposed processes yield calcium
or ammonium nitrate, both of which are hygroscopic and impart undesirable physical properties
to the fertilizer. To obtain final products containing a minimum of the highly hygroscopic
compound Ca(NO3)2, the nitrated materials are treated with controlled quantities of ammonia,
resulting in the formation of ammonium nitrate (NH4NO3) and dicalcium phosphate (CaHPO4).

The main reactions of calcium phosphate and nitric acid, calcium phosphates and mixtures of
nitric and sulfuric acids, and calcium phosphate and mixtures of nitric and phosphoric acids are
shown in equations (11), (12), and (13).

Ca3(PO4)2 + 4HNO3 = CaH4(PO4)2 + 2Ca(NO3)2…………………………………………..(11)

Ca3(PO4)2 + 2HNO3 + H2SO4 = CaH4(PO4)2 + CaSO4 + Ca(NO3)2………………..(12)

Ca3(PO4)2 + 2HNO3 + 2H3PO4 = 2CaH4(PO4)2 + Ca(NO3)2…………………………..(13)

Liquid Fertilizers
Liquid fertilizers consist of solutions of one or more highly soluble fertilizer materials.

In recent years the consumption of liquid fertilizers in the United States has expanded at a
phenomenal rate. In 1947, 47,136 short tons was used, and by 1957 the consumption rose to more
than 1,300,000 tons (mainly nitrogenous fertilizers).

From the manufacturer’s point of view, liquid fertilizer mixtures containing phosphorus, nitrogen,
and potassium have the following advantages over solid fertilizer mixtures of the same grade:

1. The manufacturing equipment required is less costly.

https://www.911metallurgist.com/properties-phosphate-rock/ 24/40
4/27/24, 5:08 PM Phosphate Rock Properties

2. Less labor is involved in handling the materials.

3. The problems of physical condition and segregation are largely eliminated.

From the farmer’s point of view, liquid fertilizers offer the advantage of being readily handled and
uniformly distributed, but the final choice between liquid and solid phosphatic fertilizers depends
chiefly on the cost of equivalent quantities of the plant-food constituents, Usually the per-unit
cost of plant food in liquid form is greater than that in dry form.

Citrate-Soluble or Available Phosphates

The term “available phosphates” is applied to certain primary and secondary products resulting
from the thermal and chemical treatment of phosphate rock. These phosphates, although virtually
insoluble in water, bring about distinct increases in crop yields. Generally their agricultural
availability is determined in the laboratory by their solubility in a neutral solution of ammonium
citrate.

Because of their limited solubility, these products usually are more effective on acid soils high in
organic matter. Under favorable conditions they dissolve at a rate commensurate with that at
which crops extract the P2O5 from the soil solution. Some authorities contend that these less-
soluble phosphates do not revert in the soil to an insoluble state as rapidly as the water-soluble
phosphates, hence their effectiveness is spread over a longer period of time.

The fertilizer materials in this category comprise such products as calcium and potassium
metaphosphate; calcined, fused, and defluorinated phosphate rock; and dicalcium phosphate.

Metaphosphates
Calcium metaphosphate (Ca(PO3)2) is a relatively new, highly concentrated fertilizer product
containing 58 to 60 percent P2O5. It is manufactured and marketed by the TVA at Wilson Dam,
Ala., by the reaction of P2O5 vapor and phosphate rock at high temperatures.

The process consists of spraying finely ground phosphate rock and elemental phosphorus into
one end of a horizontal brick-lined cylindrical chamber with an excess of air to oxidize the
phosphorus. The other end of the combustion chamber is connected with a vertical brick-lined
tower filled with phosphate-rock briquets to absorb any surplus P2O5 that does not react with the
rock dust in the combustion chamber.

At the high temperature (over 1,000° C.) developed by burning phosphorus the finely divided
phosphate rock and phosphorus pentoxide react to form a molten slag consisting essentially of
calcium metaphosphate, as shown in equation (14).

P4 + 5O2 + Ca3(PO4)2 = 3Ca(PO3)2…………………………………………………………(14)

https://www.911metallurgist.com/properties-phosphate-rock/ 25/40
4/27/24, 5:08 PM Phosphate Rock Properties

The molten calcium metaphosphate produced from the finely ground rock, as well as that formed
in the absorption tower, collects in the bottom of the combustion chamber and flows continuously
through a suitable taphole onto water-cooled steel rolls which chill and discharge it in the form of
flakes. These flakes are subsequently ground and packed in bags for shipment. A flowsheet of the
latest type of plant used in manufacturing calcium metaphosphate is shown in figure 6.

Several methods have been proposed for manufacturing potassium metaphosphate, but it has not
yet been produced on a commercial scale.

One method is to react phosphorus pentoxide with potassium chloride in the presence of water or
phosphoric acid; however, the process is intricate and difficult to control. The reaction is
represented by equation (15).

P4 + 5O2 + 4KCl + 2H2O = 4KPO3 + 4HCl……………………………………….(15)

Potassium metaphosphate is the only compound known containing 100 percent primary plant
nutrients (60 percent P2O5 and 40 percent K2O).

Dicalcium Phosphate
Dicalcium phosphate can be manufactured directly by partly neutralizing phosphoric acid or
monocalcium phosphate with lime or limestone, but little or none is produced by this process for
fertilizer use because of the cost. However, when phosphate rock is decomposed with nitric or
hydrochloric acid, the P2O5 present in the products usually is converted into dicalcium phosphate
by treatment with ammonia. Dicalcium phosphate may be left in the resultant mixture or

https://www.911metallurgist.com/properties-phosphate-rock/ 26/40
4/27/24, 5:08 PM Phosphate Rock Properties

separated by filtration. Moreover, in ammoniating superphosphate, appreciable quantities of

dicalcium phosphate are formed and remain in the product.

Because of its greater value as an animal-food supplement, dicalcium phosphate that is virtually
free from fluorine is being manufactured in substantial quantities for use as an additive to
stockfced, particularly in areas where ground and steamed bone is in short supply.

Defluorinated and Fused Phosphate Rock

Defluorinated phosphates are obtained by calcining or fusing phosphate rock with silica and/or
phosphoric acid in the presence of water vapor. At temperatures ranging from 1,400° to 1,600° C.,
the bulk of the fluorine is evolved, and the P2O5 is rendered citrate soluble. Whereas
defluorinated phosphate rock has proved to be an efficient fertilizer on acid soils, its effectiveness
on alkaline soils is somewhat doubtful. Like dicalcium phosphate, defluorinated phosphate rock
brings a high price as an ingredient of stockfeed; hence relatively little is used as fertilizer in the
United States.

Similar products are obtained by calcining or smelting phosphate rock with sodium and
magnesium salts, which break up the apatite molecule and either drive off the fluorine or combine
with it so that the final product contains P2O5 in a citrate-soluble or agriculturally available form.
Substantial quantities of these products are manufactured for fertilizer in some European
countries, but only limited quantities have been produced in the United States.

Citrate-Insoluble Phosphates
Substantial tonnages of finely ground phosphate rock are applied directly to the soil. They are
insoluble in water and only slightly soluble in carbonated water or a neutral solution of
ammonium citrate. Nevertheless, when uniformly distributed in acid soils they expose such a large
surface to the action of the soil water that the contained P2O5 is made available to crops over a
long period of time.

Finely ground phosphate rock is a soil builder for supplying P2O5 soils low in phosphate minerals.
Table 9 shows annual consumption of finely ground phosphate rock for direct application to soils,
1945-57.

https://www.911metallurgist.com/properties-phosphate-rock/ 27/40
4/27/24, 5:08 PM Phosphate Rock Properties

Other Industrial Products Derived From Phosphate

Rock
In addition to the immense tonnage of phosphate rock consumed by the fertilizer industry, large
quantities are used to manufacture phosphate chemicals to meet an expanding demand.

The fact that most of these products are relatively high grade chemicals that can best be derived
from white phosphorus accounts for the great increase in the number and size of electric-furnace
plants for extracting elemental phosphorus.

Inorganic Phosphates
As orthophosphoric acid contains three replaceable hydrogen atoms, it may be used to produce a
series of primary, secondary, and tertiary salts as typified by the following reactions:

Primary salt – H3PO4 + NaOH = NaH2PO4 + H2O

Secondary salt – H3PO4 + 2NaOH = Na2HPO4 + 2H2O

Tertiary salt – H3PO4 + 3NaOH = Na3PO4 + 3H2O

Although many inorganic compounds may be produced by treating various bases with phosphoric
acid, the phosphate salts having the widest industrial applications are those of calcium,
ammonium, and sodium.
https://www.911metallurgist.com/properties-phosphate-rock/ 28/40
4/27/24, 5:08 PM Phosphate Rock Properties

Calcium Phosphates
Substantial tonnages of relatively pure monocalcium phosphate (CaH4(PO4)2·H2O), dicalcium
phosphate (CaHPO4.2H2O), and tricalclum phosphate (Ca3(PO4)2) are consumed for uses other
than fertilizer.

Calcium phosphates are produced by the direct treatment of lime with phosphoric acid; the
successive reactions are given in equations (16), (17), and (18).

2H3PO4 + CaO = CaH4(PO4)2.H2O……………………………(16)

CaH4(PO4)2.H2O + CaO = 2CaHP04.2H2O………………..(17)

2CaHPO4.2H2O + CaO = Ca3(PO4)2 + 3H2O……………..(18)

In manufacturing monocalcium phosphate, weighed quantities of crushed lime and phosphoric

acid (75 percent H3PO4) derived from elemental phosphorus are intimately mixed in a ceramic-
lined container. The batch is maintained at a temperature of about 100° C., and much of the free
moisture is evolved during the reaction. The crystalline product is dried under controlled
conditions, crushed, and screened. The coarser granular particles are mixed with sodium
bicarbonate and starch to produce baking powder, and the finer material, is used as a leavening
agent in self-rising flours.

In recent years, anhydrous monocalcium phosphate containing small quantities of certain metallic
ions has been developed. When such a product is carefully heated, metallic ions form a coating
over the granules of monocalcium phosphate, rendering them less absorbent of atmospheric
moisture and better adapted for certain types of baked products in which a delayed leavening
action is desirable. Small quantities of monocalcium phosphate are also used in medicinal
preparations and as an ingredient of tonics designed to supply both lime and phosphoric acid.

As shown in the section on phosphatic fertilizers, dicalcium phosphate (CaHPO4.2H2O) is formed

when superphosphates are treated with ammoniacal solutions. This compound also is precipitated
when ammonia is added to the mixtures resulting from decomposition of phosphate rock with
nitric acid; however, the dicalcium phosphate thus produced usually remains in the product as a
fertilizer constituent.

Dicalcium phosphate for other industrial purposes is manufactured directly by the same general
process as that used in producing monocalcium phosphate, except that a larger proportion of
lime or limestone is used. Substantial quantities of dicalcium phosphate are also obtained as a
byproduct in manufacturing gelatin and glue from bones.

The total production of dicalcium phosphate in 1956 was about 147,000 short tons, of which over
80 percent was consumed for stock feeding. Other uses included pharmaceuticals, mild abrasives,

https://www.911metallurgist.com/properties-phosphate-rock/ 29/40
4/27/24, 5:08 PM Phosphate Rock Properties

leavening agents, and an ingredient in special types of glass.

Tricalcium phosphate is manufactured by mixing phosphoric acid with an emulsion of hydrated

lime (Ca(OH)2) in such proportions as to form a slightly basic slurry. The slurry is then pumped to
a filter press and washed with water. The damp cake is dried and milled. Tricalcium phosphate is
used principally as a mild abrasive in tooth pastes and as a conditioning agent to minimize the
caking of table salt and powdered sugar. The production of tricalcium phosphate for industrial
uses is relatively small compared with the production of other phosphates of lime. The annual
production for all purposes is estimated at 5,000 short tons.

Ammonium Phosphates
Monoammonium phosphate (NH4H2PO4) and diammonium phosphate ((NH4)2HPO4) are
crystalline salts produced directly by absorbing ammonia gas in phosphoric acid. The successive
reactions are shown in equations (19) and (20).

H3PO4 + NH3 = NH4H2PO4………………………………………..(19)

NH4H2PO4 + NH3 = (NH4)2HPO4………………………………(20)

Diammonium phosphate is less stable than monoammonium phosphate and decomposes at

temperatures above 100° C.; hence, certain precautions must be taken to prevent loss of ammonia
by overammoniation or by drying the crystals at too high a temperature.

High-grade monoammonium phosphate is made by treating phosphoric acid (75 percent H3PO4)
derived from elemental phosphorus with ammonia gas in a saturator similar to that used in
manufacturing ammonium sulfate. A pasty mass results, from which the crystalline salt is obtained
by cooling, centrifuging, and drying.

Diammonium phosphate is usually manufactured in two stages, but the TVA has developed a
continuous, single-stage saturation process for producing diammonium phosphate crystals. The
TVA process involves the continuous crystallization of diammonium phosphate from a saturated
mixture of phosphoric acid derived from elemental phosphorus and gaseous ammonia under
closely controlled temperature and acidity. The crystals of ammonium phosphate are centrifuged,
washed, and dried, and the saturated solution is returned to the circuit.

Where wet-process phosphoric acid is used, impurities such as iron, aluminum, and fluorine make
it difficult to obtain pure crystalline diammonium phosphate, but mixtures of monoammonium
and diammonium phosphate that are stable at elevated temperatures and under humid
conditions can be manufactured in granulated form.

The ammonium phosphates are being utilized to an increasing extent to manufacture

concentrated fertilizers, but they have numerous other important industrial applications.

https://www.911metallurgist.com/properties-phosphate-rock/ 30/40
4/27/24, 5:08 PM Phosphate Rock Properties

When highly heated, the ammonium phosphates evolve ammonia and are converted into tacky
masses; this fact, coupled with their high solubility, renders them useful in fire-retardant
compositions for impregnating fabrics and other combustible materials.

Monoammonium phosphate is used in yeast-culture media and to a limited extent in the dye
industry. Diammonium phosphate is used in ammoniated tooth pastes and mouthwashes.

Sodium Phosphates and Their Derivatives

By far the most important inorganic phosphate compounds used for purposes other than
fertilizers are the sodium phosphates. Monosodium phosphate (NaH2PO4), disodium phosphate
(Na2HPO4), and trisodium phosphate (Na3PO4) are produced in large quantities by the direct
treatment of soda ash or sodium hydroxide with phosphoric acid. The successive reactions are
shown in equations (21), (22), and (23).

2H3PO4 + Na2CO3 = 2NaH2PO4 + CO2 + H2O……………………………(21)

2NaH2PO4 + Na2CO3 = 2Na2HPO4 + CO2 + H2O……………………….(22)

Na2HPO4 + NaOH = Na3PO4 + H2O…………………………………………..(23)

In manufacturing trisodium phosphate, the third hydrogen atom must be displaced by sodium
hydroxide, as disodium phosphate does not react with soda ash. The solid salts for commercial
use are obtained by direct crystallization and drum drying.

Figure 7 shows a flowsheet of the trisodium phosphate process.

The main direct uses for monosodium phosphate are in boiler-water treatment and in textile
processing to control the pH. Disodium phosphate is also used for these purposes; in addition,
substantial tonnages are used in tanning leather, weighting silk, and processing cheese and in
certain medicinal products.

Virtually all of the trisodium phosphate marketed as a detergent contains 12 molecules of water of
crystallization.

https://www.911metallurgist.com/properties-phosphate-rock/ 31/40
4/27/24, 5:08 PM Phosphate Rock Properties

https://www.911metallurgist.com/properties-phosphate-rock/ 32/40
4/27/24, 5:08 PM Phosphate Rock Properties

The bulk of the monosodium and disodium phosphates are heat-treated and converted into
pyrophosphates, metaphosphates, or polyphosphates. The last-named category includes a large
number of complex products that have assumed great industrial importance.

Sodium acid pyrophosphate (NaH2P2O7), which is derived from heating monosodium phosphate
under carefully controlled conditions, is used as a leavening agent. It has mild acid properties and,
when mixed with sodium bicarbonate, is well adapted for prepared cake and doughnut mixes. A
small quantity of sodium acid pyrophosphate is used in electroplating.

When heated to a higher temperature, monosodium phosphate is converted to sodium

metaphosphate (NaPO3), a glassy product that is widely used in treating hard waters and as a
soap builder to enhance the washing properties of soaps. A flowsheet of the process for
manufacturing sodium metaphosphate is shown in figure 8.

Tetrasodium pyrophosphate (Na4P2O7) is produced by calcining disodium phosphate at a

temperature above 300° C. to drive off its water of constitution. Tetrasodium pyrophosphate is
mixed with soap powders and detergents to increase their effectiveness.

Other sodium polyphosphates are manufactured by calcining mixtures composed of different

proportions of monosudium and disodium phosphate. Before 1950, the production statistics for
sodium polyphosphates were included with those of sodium and disodium phosphate.

Sodium polyphosphates are used extensively to treat boiler feed water, and for purposes where a
detergent combining mildness and effectiveness is required.

Table 10 gives the annual production of sodium phosphates, 1941-57.

Phosphorus Chlorides, Sulfides, and Pentoxide

https://www.911metallurgist.com/properties-phosphate-rock/ 33/40
4/27/24, 5:08 PM Phosphate Rock Properties

Although a wide variety of inorganic phosphorus compounds other than phosphoric acid and its
salts can be produced from elemental phosphorus, the more important of these industrially are
the phosphorus chlorides, the phosphorus sulfides, and phosphorus pentoxide.

There are three commercially important chlorides of phosphorus: Phosphorus trichloride (PCl3),
phosphorus pentachloride (PCl5), and phosphorus oxychloride (PClO3). Phosphorus tri-chloride
and oxychloride are liquids at ordinary temperatures; phosphorus pentachloride is a crystalline
solid.

The chlorides of phosphorus are manufactured by the direct union of the elements (P and Cl) care
being taken to control the heat of the reaction by refluxing part of the product. The products are
https://www.911metallurgist.com/properties-phosphate-rock/ 34/40
4/27/24, 5:08 PM Phosphate Rock Properties

subsequently purified the trichloride by distillation and the pentachloride by recrystallization.

Phosphorus oxychloride is produced by bubbling oxygen through phosphorus trichloride or by
mixing phosphorus pentachloride with phosphorus pentoxide.

The chlorides of phosphorus are used in the manufacture of organic phosphorus compounds.
Phosphorus trichloride reacts with alcohols or phenols to form phosphite esters, and phosphorus
oxychloride under similar conditions yields phosphate esters.

Both phosphorus trichloride and phosphorus pentachloride are used as catalysts in chlorinating
certain organic compounds, particularly acids, to produce acid chlorides. Phosphorus
pentachloride in a more active chlorinating agent than the trichloride.

The two commercially important sulfides of phosphorus are phosphorus tri-sulfide (P4S3) and
phosphorus pentasulfide (P4S10), both of which are yellow solids.

Like phosphorus chlorides, phosphorus sulfides are made by direct union of the elements (P and
S). Properly proportioned charges of the two materials are stirred continuously in closed iron
containers maintained at temperatures managing from 320° to 380° C. until the reaction is
complete. The product is given ground to a powder and purified by washing it with the proper
solvent to remove any excess sulfur or phosphorus.

https://www.911metallurgist.com/properties-phosphate-rock/ 35/40
4/27/24, 5:08 PM Phosphate Rock Properties

Phosphorus trisulfide is the essential ingredient in the heads of the kitchen “strike anywhere”
matches and has entirely replaced elemental phosphorus, previously used for this purpose. Small
quantities of this compound are also used in making fireworks.

Phosphorus pentasulfide is used to prepare sulfur-bearing organic compounds and as an

ingredient of certain flotation agents. Recently, it has proved an effective additive to lubricants.
According to Van Wazer considerable work is being done on developing the organic chemistry of
its reaction products.

Three crystalline varieties of phosphorus pentoxide (P2O5) have been identified. All three forms
are decomposed by water and converted successfully into metaphosphoric, pyrophosphoric, or
orthophosphoric acid as shown in equations (24), (25), and (26).

P2O5 + H2O = 2HPO3…………………………………………(24)

2HPO3 + H2O = H4P2O7…………………………………….(25)

https://www.911metallurgist.com/properties-phosphate-rock/ 36/40
4/27/24, 5:08 PM Phosphate Rock Properties

H4P2O7 + H2O = 2H3PO4………………………………….(26)

Phosphorus pentoxide is prepared commercially by combustion of elemental phosphorus in an

excess of dried air to insure complete oxidation. The product is collected as a white, finely divided,
crystalline solid in large externally cooled chambers. The product is packed in hermetically sealed
containers to prevent it from absorbing moisture.

Because of its great affinity for water, phosphorus pentoxide is one of the most efficient drying
agents known, and this is its main industrial application. It is also used in preparing certain organic
phosphates, as it reacts with alcohols to form phosphoric acid esters.

Table 11 shows the annual production of phosphorus chlorides and phosphorus pentoxide in the
United States, 1951-57. It is estimated that 3,500 short tons of elemental phosphorus is consumed
annually in the manufacture of phosphorus sulfides.

Organic Compounds of Phosphorus

Compared to inorganic phosphates, organic compounds of phosphorus are manufactured in
relatively small quantities, but in recent years their field of usefulness has broadened considerably.

The more important organic phosphates produced on a commercial scale are the esters of
phosphoric acid. These esters are prepared by mixing phosphorus pentoxide (P2O5) or
phosphorus oxychloride (POCl3) with the appropriate alcohol or phenol in a closed vessel under
carefully controlled conditions.

https://www.911metallurgist.com/properties-phosphate-rock/ 37/40
4/27/24, 5:08 PM Phosphate Rock Properties

Certain alkyl and aryl phosphates made in this manner are excellent plasticizers. A plasticizer is a
liquid or low-melting-point solid which when added to a resin modifies one or more of the
physical characteristics of the resin. The most important function of a plasticizer is to increase the
plasticity of a resin so that it may be molded into any desired form. The mixture should be
resistant to aging, weathering, and fire.

The two principal organic phosphorus compounds used as plasticizers are tricresyl and triphenyl
phosphates. Their use has expanded substantially with the phenomenal growth of the plastic
industry. These organic phosphates are being used in increasing quantities as additives in
hydraulic fluids and other oils. They not only serve as dispersing agents, corrosion inhibitors, and
antioxidants but also are lubricants.

In recent years some esters of phosphoric acid have proved to be highly efficient insecticides in
controlling aphids and mites. One such compound is tetraethyl pyrophosphate (TEPP), the
production of which reached 515,000 pounds in 1955.

The organic reaction products of phosphorus pentasulfide, such as the dialkyl ester of
dithiophosphoric acid (R3PO2S2) and its related salts, are effective flotation agents for recovering
certain metals from their ores.

Table 12 gives the production of some of the more important phosphoric acid esters, 1951-57.

Phosphate Products
The phenomenal expansion of the phosphate industry during the past 15 years or more may be
attributed to the following factors:

https://www.911metallurgist.com/properties-phosphate-rock/ 38/40
4/27/24, 5:08 PM Phosphate Rock Properties

1. The increased use of phosphatic fertilizers.

2. New and expanded outlets for phosphate-products other than fertilizers.
3. Improvement in techniques for processing phosphate rock.

According to figures of the U.S. Department of Agriculture, the harvested acreage of crops in the
continental United States in 1955 was only about 2 percent greater than in 1940, yet the output of
agricultural products in 1955 not only was sufficient to meet the needs of a population that had
increased more than 25 percent but provided a large surplus.

Although the greater yield of crops per acre was due to a number of factors, it is highly significant
that the annual consumption of fertilizers in this 15-year period rose from 8,656,000 to 22,500,000
tons, an increase of 160 percent.

New industrial uses for relatively pure inorganic phosphate salt, particularly in the detergent field,
have provided a large market for such products. Certain organic phosphates also have been
developed that are of great importance in the plastic industry, as additives to motor fuel, and in
the manufacture of insecticides.

Improvements in mining and processing techniques have allowed the utilization of lower grade
phosphatic raw materials that formerly were considered economic. More efficient procedures in
the electric smelting of phosphate ores for recovering phosphorus and subsequently converting it
into phosphoric acid are among the outstanding developments contributing to the wider use of
phosphate compounds. Even when such plants are far from consuming centers, the shipment of
elemental phosphorus and concentrated phosphoric acid to distant markets has proved
economically feasible.

The outlook for further expansion of the phosphate industry is favorable although it is doubtful if
the upward trend will continue at the rate of the past 15 years.

Crop production, however, must keep pace with the increasing population of the United States,
and this can be accomplished on a limited acreage only by intensive fertilization.

Although there is little doubt that other industrial uses will be found for both organic and
inorganic phosphates, it seems unlikely that such uses will create a demand comparable to that
resulting from the use of phosphates in detergents.

There are, however, promising possibilities of effecting further improvements in processing

techniques. Moreover, better recovery and utilization of byproducts would reduce the net cost of
manufacturing phosphate compounds and provide an additional incentive to expand
manufacturing facilities.

https://www.911metallurgist.com/properties-phosphate-rock/ 39/40
4/27/24, 5:08 PM Phosphate Rock Properties

by David February 18, 2021 Uncategorized 960

Copyright 2012-2021 911Metallurgist | All Rights Reserved

About us | Privacy | Contact Us

https://www.911metallurgist.com/properties-phosphate-rock/ 40/40