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1.2. Production
IG Process [6]. In the IG process (Fig. 7), The orthophosphoric acid obtained is virtu-
phosphorus combustion and P4 O10 absorption ally free of lower phosphorus oxides and its
are carried out in a single stage in a common H3 PO3 content is 0.1 %.
tower. The tower walls are slightly conically in- Thermal phosphoric acid contains only traces
clined so that the recycled acid, overflowing in- of impurities due to the use of pure phosphorus
side from a cup located at the tower head, can for combustion. Only arsenic, a natural compan-
completely cover the wall with an acid layer. ion of elemental phosphorus which is contained
This protects the wall from the phosphorus flame in the acid at a concentration of 5 –30 ppm, need
that descends from the tower head and reaches be removed in a further purification step. This is
a temperature > 2000 ◦ C. The recycling phos- accomplished by precipitation of arsenic sulfide
phoric acid dissolves the phosphorus pentoxide with hydrogen sulfide followed by filtration. The
formed and dissipates the heat from the reaction hydrogen sulfide is generated by injecting Na2 S
zone. It is collected below the acid tower and solution into the phosphoric acid. This is done
recycled to the tower cup after passing through either in a precipitation tower with subsequent
the heat exchanger. filtration after addition of activated charcoal and
Phosphoric acid overflows from the tower cup kieselgel [8], or more directly and simply in a
at ca. 60 ◦ C and is heated on the way along the centrifugal pump which immediately conveys
tower walls to up to 85 ◦ C. About 80 % of the the acid to the filter [9].
heat generated is dissipated by the cooling wa-
ter, 17 % by off-gas and water evaporation, and TVA Process [10]. In the Tennessee Valley
3 % by the sensible heat of the acid. Authority (TVA) process phosphorus combus-
The phosphorus is sprayed into the tower tion and P4 O10 absorption are carried out sepa-
from a binary nozzle by pressurized air or steam rately (Fig. 8).
at up to 1.5 MPa. It is ejected from the nozzle at The vertical, cylindrical, stainless steel
such a high speed that the phosphorus flame is phosphorus combustion chamber is externally
kept away from the head and cannot damage it. A cooled. The phosphorus burner is installed lat-
slight underpressure is maintained in the tower, erally and is directed downwards toward the bot-
generated by a fan which draws the combustion tom of the combustion chamber at an angle of
air from an annular aperture around the nozzle ca. 40◦ .
at the tower head. The off-gas is discharged in The gas discharge and the connection to the
the wash stage. Here, P4 O10 that is entrained in absorption tower are located at the top of the
the off-gas in the form of aerosol or acid droplets combustion chamber. A layer of polyphosphoric
is separated. It accounts for ca. 30 % of the to- acid is formed from generated P4 O10 and atmo-
tal conversion. The wash acid is added to the spheric moisture, which protects the inner walls
tower acid. Venturi systems, wash towers oper- against corrosion. The polyphosphoric acid con-
ated with or without packing, or demister ele- tains ca. 92 % P2 O5 , and its vaporization point
ments packed with glass fibers are used as sep- is 867 ◦ C. Phosphorus and air are introduced in
arators [7]. a manner similar to the IG process.
All parts of the equipment which come into The stainless steel cylindrical absorption
contact with P4 O10 -containing off-gases are tower with a conical head is also externally
made of rubber- coated steel, stainless steel, or cooled. The inner tower walls are sprayed with
plastic. A stainless steel with very low carbon dilute phosphoric acid from the off-gas purifica-
content, stable against concentrated phosphoric tion stage and with recycled, concentrated phos-
acid at up to 100 ◦ C, has prevailed as construc- phoric acid such that an unbroken acid film is
tion material for the acid tower. formed. The phosphoric acid so produced con-
In addition to the phosphoric acid flowing tains 54 – 83 % P2 O5 .
down on the tower walls, phosphoric acid is A significant part of the P4 O10 product is
sprayed into the tower through nozzles in the entrained in the gas flow from the absorption
lower tower half below the phosphorus flame tower. Thus, depending on whether the prod-
and perpendicular to the off-gas flow. This de- uct is orthophosphoric acid (54 % P4 O10 ) or
creases the off-gas temperature to ca. 100 ◦ C. superphosphoric acid (83 % P4 O10 ), 40 – 70 %
of the acid produced accumulates in the gas pu-
Phosphoric Acid and Phosphates 5
rification stage. Venturi scrubbers, wash towers, steam generation. Phosphorus combustion and
and demisters with webs made of special steel P2 O5 hydration are performed separately.
are used for flue-gas purification. Liquid phosphorus and dried air are injected
into the bottom of a vertical stainless steel com-
Hoechst Process [11]. The heat generated bustion chamber and are combusted to give
by combustion of phosphorus is unused and is P4 O10 . The walls of the combustion chamber
dissipated by cooling in the IG and TVA pro- are made of pipe coils through which deion-
cesses. In the Hoechst process (Fig. 9), operated ized water is pumped. The steam – condensate
industrially since 1989, this energy is used for mixture formed in the coils by dissipation of
the heat of combustion is kept at a pressure of
6 Phosphoric Acid and Phosphates
Calcium sulfate can precipitate in three dif- [12], [13]. Round models (see Fig. 11) as well as
ferent modifications, depending on the tem- rectangular ones were constructed. In the round
perature and the phosphoric acid concentration single tank, the reaction components are slowly
(Fig. 10). The designation of the various wet pro- moved in a circle in the outer, annular space
cesses is derived from the modification formed with vigorous, local agitation. Part of the di-
in the digestion stage. Thus, dihydrate (DH) and gestion slurry overflows into the central space
hemihydrate (HH) processes are distinguished. and flows to filtration. In medium-sized facili-
In other processes, two crystalline forms are ties (200 – 400 t/d P2 O5 ), air is blown onto the
formed sequentially and separated by recrystal- surface for dissipation of the heat of reaction
lization (HH/DH or DH/HH processes). (2 GJ/t P2 O5 in a DH process). In larger plants,
the heat is dissipated by vacuum evaporation of
water from a recycled partial stream of the slurry
in a flash cooler [14], [15].
UCEGO [13], [15], [17], [18]). The effective fil- temperature in the stability range of calcium
ter area can approach up to 200 m2 . Later, band sulfate hemihydrate (see Fig. 10). Thus, single-
filters with larger outputs and filter areas ex- stage (HH) and two-stage (HH/DH, DH/HH)
ceeding 100 m2 became available. In the filtra- processes were developed in which the hemihy-
tion, the wet phosphoric acid is drawn off from drate is formed as end or intermediate product.
the solids in a partial vacuum. Adhering acid The first commercial HH/DH process was
is washed off the solids in two or three stages introduced in Japan. The major interest in this
in countercurrent. The wash acid is discharged process was the production of pure gypsum that
separately and recycled to the reactor. The dis- could be used for cement production since there
charge of the filter cake is carried out by tilting are no natural gypsum deposits in this region.
the filter pans, by means of a screw conveyor, or Around 60 hemihydrate plants operated
by stripping from the band. worldwide; more than half of them use a HH/DH
Due to technical progress in reactor and fil- process. The single-stage HH process has sel-
ter construction, production units for wet phos- dom been used because of the unfavorable pro-
phoric acid now have capacities up to 1000 t/d cess yield.
of P2 O5 . The various processes and some typical fea-
tures are as follows:
Dihydrate Process. The dihydrate process is
the classical method for the production of wet 1) HH Process [19]
phosphoric acid (Fig. 12). Prior to digestion, the Features:
phosphate rock must usually be ground to a fine- Single filtration stage
ness of 75 % < 150 µm. Phosphate rock and con- Impure CaSO4 · 1/2 H2 O
centrated sulfuric acid are charged spatially sep- Yield, 90 – 94 %
arated. In this way, the concentration of sulfuric Phosphoric acid, 40 – 48 % P2 O5
acid is lowered so that the digestion occurring
at the phosphate rock charging point is not hin- 2) HH/DH Process [20]
dered by formation of a gypsum layer on the a) Without intermediate separation of the
ore particles. In addition, the formation of too hemihydrate
many gypsum seed crystals due to supersatu- Features:
ration of Ca2+ and SO− 4 ions is avoided. The Single filtration stage
calcium sulfate is present as the dihydrate at a Pure CaSO4 · 2 H2 O
reaction temperature of 70 – 80 ◦ C and a phos- Phosphoric acid, 30 – 32 %P2 O5
phoric acid concentration of 28 – 31 %. Usually, b) With intermediate separation
the filtered acid is further concentrated (see Sec- Features:
tion 1.2.3). Two filtration stages
Advantages of the dihydrate process are the Very pure gypsum
low reaction temperature and, therefore, fewer Yield, 98.5 %
corrosion problems; its applicability to most Phosphoric acid, 40 – 52 % P2 O5
grades of phosphate rock; and its suitability for
large-volume production. Some disadvantages Figure 13 shows the flow sheet for the Fison
are the production of a comparatively dilute process as an example of a HH/DH process with
phosphoric acid which must subsequently be intermediate separation of the hemihydrate [14].
concentrated; the need to grind the phosphate In this two-stage processes, the higher digestion
rock; and the relatively high P2 O5 losses of 4 – temperature of 85 – 110 ◦ C increases the reac-
6 % in the gypsum. tion rate and allows the use of unground phos-
phate rock.
Hemihydrate Process. Rising energy costs Depending on the process, the conversion of
initiated the development of processes that allow the hemihydrate is carried out under different
the production of phosphoric acid with 40 – 50 % conditions. In the Nissan process, which dis-
P2 O5 , without using additional concentration penses with the intermediate separation of hemi-
steps, for direct use in fertilizer production. hydrate, the dihydrate is crystallized after cool-
These processes must be carried out at higher ing of the digestion slurry from 85 – 90 ◦ C to
Phosphoric Acid and Phosphates 9
55 –65 ◦ C [20]. In the Fison process the hemi- This process is only of interest where very
hydrate is recrystallized after filtration from high purity hemihydrate is required, for exam-
a washing acid (a mixture of sulfuric and ple, in plaster.
phosphoric acid: 4 – 8 % SO3 , 10 – 20 % P2 O5 )
slurry.
1.2.3. Concentration of Wet Phosphoric
Acid
3) DH/HH Process [14], [21]
Features: Most of the wet phosphoric acid produced
Repeated filtration with intermediate worldwide is made by the dihydrate process. For
conversion further processing to fertilizers, the major appli-
Very pure CaSO4 · 1/2 H2 O cation (→ Phosphate Fertilizers), the concentra-
Yield, 96 – 98 % tion of the phosphoric acid must be increased
Phosphoric acid, 32 – 36 % P2 O5 from 28 – 30 % P2 O5 to 40 – 55 % or even 70 %
P2 O5 (superphosphoric acid). Submerged com-
10 Phosphoric Acid and Phosphates
bustion burners and vacuum circulation evapora- Depending on the further application, these
tors are customary concentration devices. In the impurities must be partially or completely re-
older submerged burner process, hot combustion moved from crude phosphoric acid. Precipita-
gases from an oil burner are blown through a dip tion and extraction processes are used.
tube or directly into phosphoric acid [22]. At an
acid temperature of 350 ◦ C, the off-gases entrain
high proportions of phosphoric acid as aerosols
as well as volatile fluorine compounds. Purifica-
tion of these off-gas streams is expensive.
Today, submerged combustion burners are
still in use only in older plants. Currently, vac-
uum evaporation with forced circulation is the
concentration method generally used (Fig. 14).
Depending on the amount of water to be evapo-
rated, one or more evaporators are used in paral-
lel or in series. Multistage evaporators arranged
in tiers of usually three stages have the advan-
tage of lower energy costs. The energy savings
result from effective heat utilization. The vapors
of an evaporator stage operated at a higher tem-
perature are used for heating another operated at
a lower temperature [23]. In the concentration of
phosphoric acid from 30 to 50 % P2 O5 , the steam
requirements can be reduced from 1.25 t to 0.7 t
per tonne of evaporated water. Rubber-proofed Figure 14. Recycling evaporator for concentration of wet
steel is the predominant material of construction phosphoric acid
a) Recycle evaporator; b) Circulation pump; c) Heat ex-
for containers, piping, and pumps at operating changer; d) Condenser; e) Product takeoff; f ) Pump
temperatures below 120 ◦ C. At higher tempera-
tures, e.g., in the production of superphosphoric
acid at up to 200 ◦ C, alloys such as Hastelloy Precipitation Processes. The separation of
alloy G 3 or Sanicro 28 are used. The heat ex- arsenic and, to an increasing extent, of cadmium
changer tubes are usually made of graphite or is required for the use of wet phosphoric acid in
nickel alloys. fertilizer production. For separation of arsenic,
Apart from water vapor, a mixture of SiF4 and a Na2 S solution is added to the crude acid, and
HF is generated during the concentration of wet the precipitated arsenic sulfide is removed by
phosphoric acid. About 50 – 60 % of the fluorine filtration.
content of wet phosphoric acid is volatilized on The separation of cadmium by means of a
concentration from 30 to 55 % P2 O5 . In order to complexing agent such as alkyldithiophosphoric
comply with the fluorine emission limits of the acid alkyl ester [25] can also be classified as a
plant or to obtain a salable coproduct, concentra- precipitation reaction because the precipitated
tion units are equipped with facilities for the pro- cadmium complex is separated in solid form ei-
duction of H2 SiF6 . Thus, 90 – 95 % of the gen- ther directly or after addition of a filter aid or ab-
erated fluorine can be converted to a 15 – 25 % sorbent. Such a process is operated on a commer-
H2 SiF6 solution [24]. cial scale by Tessenderlo Chemie in Belgium.
Further purification of wet phosphoric acid
by precipitation of cationic impurities, espe-
1.2.4. Purification of Wet Phosphoric Acid cially Fe, Al, Mg, and Ca, is possible by neu-
tralizing the acid with caustic soda. The precip-
Wet phosphoric acid produced by wet digestion itated metal phosphates are filtered under pres-
contains variable amounts of inorganic impuri- sure from the resulting sodium phosphate solu-
ties, depending on the origin of the phosphate tion, which contains 18 – 20 % P2 O5 . In order
rock. to decrease P2 O5 losses in the filter cake from
Phosphoric Acid and Phosphates 11
> 10 % to < 5 %, [26] the filter cake is worked anionic components such as SO2− 4 or F− are
up with more caustic soda to give a trisodium also removed with the metal cations. The wash
phosphate solution and precipitatable metal hy- extract–phosphoric acid enriched in impurities–
droxides. Since the phosphoric acid in this neu- is recycled to the extraction stage. The phos-
tralization process is converted to a phosphate phoric acid product is obtained from the purified
salt solution, its uses are limited. For instance, extract by addition of water or by distillation of
wet phosphoric acid is used for the production solvent. If further processing of the acid to com-
of detergent phosphates (pentasodium triphos- mercial phosphates is intended, a phosphate salt
phate, see Section 3.2.3) via this route in West- solution can be obtained directly by addition of
ern Europe. alkalies to the extract. The recovered solvent is
recycled to the extraction stage. Usually, a partial
Extraction processes are the predominant stream is purified, for example, by distillation.
methods for the purification of wet phosphoric Generally, stripping for complete solvent sep-
acid. Processes are operated for the separation of aration and concentration of the phosphoric acid
single components as well as of practically all to 50 – 70 % P2 O5 are among the posttreatment
impurities in wet phosphoric acid. However, this steps. In these operations, the fluoride content of
complete purification includes measures (e.g., the acid is also further decreased. Pressure strip-
acid discoloration and removal of traces of ar- ping of the acid with steam to decrease the fluo-
senic and fluorine) which supplement the extrac- ride content to <10 ppm and oxidative degrada-
tion process. The quality of such purified phos- tion of organic trace impurities are used for the
phoric acid equals that of thermally produced production of food-grade phosphoric acid.
acid. The choice of solvent is an important feature
In 1990, production capacities for extrac- of the extraction processes. With solvents that
tively purified P2 O5 amounted to 740 000 t/a are infinitely miscible with water, such as iso-
worldwide, including 300 000 t/a in Western Eu- propanol [27], extraction may be complete in
rope. one or two stages. Alkali-metal or ammonium
The basic concept for extractive purification ions are added for better development of the or-
of wet phosphoric acid is the same in all pro- ganic and aqueous phases. Phosphoric acid is
cesses. Figure 15 shows a schematic of the pu- recovered from the extract by solvent distilla-
rification steps. Crude wet phosphoric acid con- tion.
taining 40 – 50 % P2 O5 is prepurified in order Frequently, alcohols that are partially mis-
to largely separate, if necessary, arsenic, sul- cible with water, such as butanol [7] or amyl
fate, and organic components by precipitation alcohol [28], [29], are used. Six- to ten-stage
or adsorption. In the subsequent extraction pro- mixer –settler units are used to attain essentially
cess, prepurified acid is contacted with solvent quantitative phosphoric acid extraction.
countercurrently in several stages. Together with The IMI process, developed for the extraction
small amounts of impurities, the phosphoric acid of phosphoric acid from phosphate rock digested
is transferred to the organic phase, while most of with hydrochloric acid, is a special case [28]:
the impurities remain in the aqueous phase. If a CaCl2 is added as extraction aid to increase the
high yield of P2 O5 (95 – 98 %) is desired, sulfu- equilibrium concentration of phosphoric acid in
ric acid is added during the extraction so that the the alcoholic phase.
cationic impurities remain in the aqueous phase Methyl isobutyl ketone (MIBK) [30], tributyl
as sulfates. In addition, so-called splitting pro- phosphate [31], diisopropyl ether [7], or mix-
cesses are customary. In these, only 50 – 70 % of tures of the latter two [32] are immiscible with
the phosphoric acid are extracted in simple plant. water. Usually, the processes based on these sol-
Phosphoric acid contained in the aqueous phase, vents are splitting processes without quantitive
together with the impurities, is treated further in P2 O5 extraction. The use of diisopropyl ether
fertilizer production. for extraction and reextraction is based on the
The crude extract containing the phosphoric temperature dependent solubility of phosphoric
acid is washed countercurrently with small acid in this solvent. Extraction is carried out at
amounts of water, phosphoric acid, or phosphate 0 – 5 ◦ C, and the acid is reseparated after addi-
salt solutions. Depending on the wash liquid, tion of a small amount of water at 30 ◦ C.
12 Phosphoric Acid and Phosphates
Extraction of Single Components. The mand for wet phosphoric acid for further pro-
first commercial processes for the separation cessing to fertilizers. As shown in Figure 16 for
of single components involved the production the United States, the world’s largest producer
of uranium, which can be present in wet phos- and consumer of wet phosphoric acid, its share
phoric acid at concentrations of up to 200 ppm. of the total phosphoric acid production amounts
Large industrial plants were first operated in the to more than 90 %. Besides the fertilizers area,
1950s with alkyl diphosphate esters [33], and in industrial phosphates (see Chap. 3) and feedstuff
the 1970s improved processes with octyl phenyl are other areas of application of wet phosphoric
phosphate esters, octyl diphosphate esters [34], acid.
or mixtures of di-2-ethylhexyl phosphate and
tri-n-octyl phosphine oxide [35], [36] were in-
troduced. However, these extraction plants were
closed after several years of operation, mainly
because of declining uranium prices. Only in
Belgium is uranium still produced extractively
from wet phosphoric acid by Prayon [37].
A process developed for the removal of cad-
mium involves prepurification of the acid to sep-
arate solids and subsequent extraction of cad-
mium into an organic phase [38]. Alkylamines
are used as extractive agents in the presence of
halide ions (Cl− , I− , Br− ). In the reextraction
stage, cadmium is transferred back to the aque-
ous phase. Cadmium is precipitated and sepa-
rated from this solution as the sulfide. Figure 16. Phosphoric acid production in the United States
gle product, although purified wet phosphoric Table 1. Typical phosphogypsum analyses (%)
acid is being used increasingly for its produc-
tion. Thermal acid is used in metal surface treat- Production process
ment (→ Metals, Surface Treatment, Chap. 3.) Dihydrate Hemihydrate Hemi-/
and, in food-grade quality, for the acidulation of dihydrate
beverages. CaO 32.50 36.9 32.20
After decades of strong growth, a decrease SO3 44.00 50.3 46.50
of worldwide phosphoric acid production oc- P2 O 5 0.65 1.5 0.25
curred in the 1980s (see Fig. 16). Ecological F 1.20 0.8 0.50
SiO2 0.50 0.7 0.40
problems related to rising phosphate consump- Fe2 O3 0.10 0.1 0.05
tion are an essential cause of this development. Al2 O3 0.10 0.3 0.30
Among these are the impairment of subsoil wa- MgO 0.10
H2 O 19.00 9.0 20.00
ter by phosphate fertilizers and the eutrophica-
Process yield,
tion of surface waters by phosphates from fer- t/t P2 O5 4.9 4.3 4.9
tilizers and detergents. These ecological pres-
sures have already resulted in extensive replace-
ment of phosphate-containing detergents and a The disposal of gypsum from production fa-
decrease in the use of mineral fertilizers in agri- cilities near the sea is usually by outflow into
culture. the sea. Three aspects for the evaluation of
the ecological consequences must be consid-
ered: (1) the large amounts of gypsum involved,
(2) traces of heavy metals in the gypsum, and
1.4. Environmental Aspects
(3) changes in the pH of the water due to resid-
ual phosphoric and hydrofluoric acids.
Phosphoric acid is now mainly produced (ca.
The solubility of calcium sulfate in water is
95 %) by the wet process. Because of the high
2.4 g/L; in seawater it is ca. 3.5 g/L [42]. Seawa-
energy consumption, only ca. 5 % is produced by
ter naturally contains 1.6 g/L calcium sulfate, so
the thermal process. An overview of the world-
that, given sufficient tidal and natural movement
wide capacity in 1989 (40.6×106 t P2 O5 ) is
of the water, a rapid dissolution of the gypsum is
given in [39]. Gypsum and fluoride are the main
observed. SiO2 , Al2 O3 , and organic constituents
byproducts of the wet process; phosphorus slag
remain undissolved.
is a byproduct of phosphorus production by the
The amount of heavy metals added to seawa-
electric furnace process.
ter due to phosphogypsum is relatively small in
comparison to the existing levels; see Tables 2
Phosphogypsum. A quantity of 4.5 – 5.5 t
and 3 [43], [44]. Hence, there is no enrichment
impure calcium sulfate is obtained as byprod-
of heavy metals in seawater due to this disposal
uct during the production of 1 t P2 O5 by the wet
method. The enrichment of the highly toxic
process. In 1988, 27.7×106 t P2 O5 were pro-
heavy metal cadmium in the environment as a
duced and hence ca. 140×106 t gypsum. Dis-
result of industrial emission is, however, viewed
posal of these large amounts of gypsum is caus-
critically. As the result of a study [45], cad-
ing considerable problems, especially from an
mium will be subject to increasing strict emis-
environmental and ecological viewpoint [40].
sion limits, for example, in the Netherlands [46].
The gypsum contains production- and source-
The amount of cadmium in phosphogypsum dis-
specific constituents (Table 1) [41]. Three pos-
charged into seawater in the EC in 1979 was 62 t
sibilities for the disposal of phosphogypsum ex-
[47].
ist:
The pH of a 10 % phosphogypsum sus-
1) Dumping at sea (10 %) pension in water is 3.3. Seawater is buffered
2) Dumping on land (ca. 88 %) by hydrogencarbonate ions and has a pH of
3) Use as a raw material 7.9. Therefore, the introduction of even large
amounts of slurry cannot cause the pH to drop
below the critical level of 5.5 [48]. However, par-
ticular attention must be paid to the effects of
14 Phosphoric Acid and Phosphates
dumping gypsum in the sea. Permanent surveil- Due to the large amounts of phosphogypsum,
lance of the effects of the dumping (especially the sensitivity with regard to environmental
with regard to accumulation) on marine flora and problems, and the scarcity of dumping areas, the
fauna must be carried out. following attempts have been made to use it as
a raw material [54]:
Table 2. Trace elements in phosphate rock from Morocco and Florida
and percentages thereof in phosphogypsum 1) Use as building material (e.g., plasterboard)
Element Morocco, Florida, Percentage in 2) Cement additive
ppm ppm phosphogypsum 3) Use in agriculture
Cadmium 17 10 15 – 25
4) Use as a filler in the paper industry
Chromium 150 ≤ 90 5 – 10 5) Recycling to sulfuric acid and cement
Copper 28 5 – 20 4–8
Manganese 10 min. 100 10 – 15 The use of large amounts of phosphogypsum
Nickel 16 25 – 75 25 – 50 as raw material is generally only of economic
Uranium 120 200 15 – 20
Zinc 200 10 4–8
interest in countries that do not have any natu-
ral source of gypsum. Examples are Japan and
South Korea, where ca. 3×106 t of phospho-
gypsum is used, mainly in the cement industry.
Table 3. Trace elements in seawater
Otherwise only small amounts are utilized. Rea-
Element Concentration, kg/km3 sons include the impurities, the water content,
Chromium 48
the transport costs, the low price of high-purity
Cadmium 120 natural gypsum, and the increased accumulation
Copper 3 360 of gypsum from flue gas desulfurization [55].
Manganese 2 160
Nickel 2 160
Uranium 3 360 Fluoride. Phosphate ore contains ca.
Zinc 11 280 3.6 – 4.1 % fluoride that–depending on the
process–is distributed in various amounts among
the acid, in the phosphogypsum, the reactor off-
The dumping of phosphogypsum proceeds in gas, and the off-gases from cooling or concen-
two ways: tration of the acid (Table 4) [56].
1) The gypsum is slurried with water and then
pumped to settling vessels. The used wa- Table 4. Distribution of fluoride in the production of wet phosphoric
acid
ter is generally recycled [49]. This disposal
method is used especially in the United Dihydrate Hemihydrate
process, % process, %
States. Problems can arise due to the diffi-
culty of evaluating the emission of fluoride Acid 15 12
and of seepage water containing phosphate Phosphogypsum 45 50
Reactor off-gas 5 8
and other constituents [50]. Here, too, su- Flash cooler vapor 30
pervision of the ecological effects should be Concentration vapor 35
considered [51]. In Sweden an artificial is-
land has been developed for the dumping of
gypsum [52]. Because of its damaging effects on the en-
2) The dried gypsum (residual water content vironment [57] fluoride from off-gases is either
20 % min.) is stored in a dump. Another pos- precipitated in a basic wash as CaF2 or in an acid
sibility is the filling of empty brown coal wash as fluorosilicate [58]. Depending on the de-
mines with protection of the groundwater by mand the CaF2 or fluorosilicate is either utilized
confining the dried gypsum with polyethyl- or dumped. In Germany the maximum emission
ene sheets [53]. values for the off-gas [59] are 50 mg/m3 for solid
For the disposal of dried phosphate sludge, particles and 5 mg/m3 for gaseous fluorine com-
special isolated disposal sections and treatment pounds.
of seepage water should be undertaken to avoid
environmental risks.
Phosphoric Acid and Phosphates 15
Phosphorus Furnace Slag. Eight tonnes of ion exchange, or by reaction of insoluble lead
slag are obtained during the production of 1 t pyrophosphate with hydrogen sulfide.
of phosphorus by the furnace process. The slag, Unlike monophosphoric acid, aqueous solu-
which consists mainly of calcium silicate, is ob- tions of pyrophosphates do not give a yellow pre-
tained as lumps or granules. cipitate with silver nitrate but a white one. Com-
Typical percentage slag composition is as fol- pared with metaphosphoric acids, which also
lows: form a white precipitate, pyrophosphate differs
P2 O 5 1.0
in that it does not coagulate albumin.
CaO 48.4
SiO2 42.5 Polyphosphoric and Metaphosphoric
F 3.3 Acids. In low-molecular, linear polyphosphoric
Al2 O3 2.5
Fe2 O3 0.2 acids (n = 2 – 15) such as tetraphosphoric acid,
MgO 0.6 H6 P4 O13 ,
Na2 O 0.9
K2 O 0.5
16
Total Number of P atoms in the low-molecular polyacids Highly Trimeta Tetra-
condensed meta
P4 O10 , % 1 2 3 4 5 6 7 8 9 10 11 12 13 14
67.4 100.0
68.7 99.7 0.33
70.4 96.2 3.85
71.7 91.0 8.86 trace
73.5 77.1 22.1 0.79
73.9 73.6 25.1 1.34
75.7 53.9 40.7 4.86 0.46
77.5 33.5 50.6 11.5 2.86 0.74 trace
79.1 22.1 46.3 20.3 7.82 2.26 1.02 0.34
80.5 13.8 38.2 23.0 13.0 6.86 3.38 1.67 1.03 0.22
81.0 12.2 34.0 22.7 14.6 8.42 4.36 2.27 1.41 0.56 trace
81.2 10.9 32.9 22.3 15.0 9.36 5.41 2.85 1.75 0.97 0.36 0.05
82.4 7.32 23.0 19.3 15.9 12.3 8.21 5.73 3.89 2.52 1.36 0.91 0.14 trace
84.0 3.92 11.8 12.7 12.0 10.5 8.97 7.99 6.62 5.63 4.54 3.72 3.03 2.46 1.68 6.63
85.0 2.28 6.36 7.32 8.01 8.17 7.67 7.22 6.93 6.42 5.89 5.27 4.69 3.99 3.83 16.9
85.3 1.87 4.73 6.33 6.58 6.66 6.71 6.36 6.11 5.88 5.46 5.07 4.90 4.64 4.38 25.6
Phosphoric Acid and Phosphates
86.1 1.46 2.81 3.74 4.43 4.52 4.77 4.79 4.93 4.67 4.54 4.67 4.63 4.38 4.17 43.5 trace
87.1 0.83 1.81 2.17 2.53 3.09 3.39 3.46 3.33 3.55 3.47 3.45 3.52 3.26 3.24 61.1 trace
87.9 0.50 0.82 1.56 1.76 1.72 2.03 2.13 2.26 2.07 2.26 2.06 2.20 1.99 2.30 76.4 0.42 0.11
89.4 1.88 1.52 0.7 0.61 0.62 0.68 0.54 0.71 0.36 1.03 0.98 1.16 1.23 1.37 86.8 1.17 0.41
Phosphoric Acid and Phosphates 17
deposit on pipes and containers unless during plication of polyphosphoric acids until about
shipment and storage the acid is constantly agi- 1973. Especially in the United States, large
tated. Because polyphosphoric acid has a higher amounts of ammonium phosphate, triple super-
lime-binding strength, the impurities are held in phosphate, and liquid fertilizers were made from
solution and cannot deposit. polyphosphoric acids. This application has de-
Phosphoric acid plants in which combustion clined strongly. Polyphosphoric acid is used in
of phosphorus and absorption of P2 O5 vapors are organic chemistry as an acidic catalyst and dehy-
performed separately are best suited to the ther- drating agent as well as for cyclization reactions
mal production of polyphosphoric acid (see TVA [69].
process, page 6). An externally water-cooled
tower made of stainless steel is used for combus-
tion. A hydration tower, also made of stainless 3. Phosphates
steel, cooled externally with water and internally
with recycled acid, is used for the absorption The salts of phosphoric acid are technically
of P2 O5 mist. The phosphoric acid recycled in and commercially the most important group
the hydration tower can be kept at the concen- of phosphorus compounds besides the acid it-
tration of the desired polyphosphoric acid if an self. According to their applications, fertilizer
appropriately intensive cooling facility is avail- phosphates (→ Phosphate Fertilizers) are dis-
able [67]. A polyphosphoric acid plant differs tinguished from other commercial phosphates
from an orthophosphoric acid plant by more ex- discussed here. While the use of phosphates as
pensive cooling and circulation equipment be- fertilizers started in the mid-1800s with the in-
cause, in contrast to orthophosphoric acid pro- troduction of mineral fertilization, other phos-
duction, water evaporation cannot be used as a phates were used industrially at the turn of the
contribution to cooling capacity during produc- century only sporadically. They attained greater
tion of polyphosphoric acid, and the viscosity of commercial importance since ca. 1930 with the
polyphosphoric acid is much higher than that of production of condensed phosphates, especially
orthophosphoric acid. for the detergent industry.
In another process, polyphosphoric acid is
produced in a tower in which phosphorus is com- Structure and Nomenclature. All phos-
busted and P2 O5 mist is absorbed (cf. IG pro- phate salts contain PO4 units as characteris-
cess, page 4). The tower consists of two sections tic structural element. The central phosphorus
of different diameters so that a step is formed atom is surrounded by a tetrahedral arrangement
at the joint, which serves as an acid collection of oxygen atoms. The tetrahedral symmetry is
cup. A second collection cup is located below based on formation of sp3 hybrid orbitals on the
the tower. phosphorus atom, which is linked to the four
The tower walls are protected by two phos- oxygen atoms by sigma bonds. The P – O bond
phoric acids of different concentrations. In the strength is enhanced by π bonding with partici-
upper section, polyphosphoric acid containing pation of phosphorus d orbitals. Ideal tetrahedral
76 % P2 O5 flows from an overflow cup down structure with a theoretical O – P – O bond angle
the tower walls. In the lower section, polyphos- of 109◦ 28 can only be expected for a free PO3−
4
phoric acid with 84 % P2 O5 is sprayed onto ion. In most crystalline phosphates, especially
the tower walls. Both acid recycle streams are in condensed phosphates, deformation of the
cooled by cooling facilities. It is advantageous to PO4 tetrahedra occurs due to unsymmetrical
operate this plant in combination with other pro- lattice forces, so that bond angles of 95 – 125◦
duction units for phosphoric acid. Such a plant are found. The bond lengths are shorter than ex-
can for instance use the flue gases from produc- pected for a single bond due to the double bond
tion of dry P2 O5 and pass its own flue gases on character. Average P – O distances of 154 pm
to the absorption section of the orthophosphoric are found.
acid plant [68]. Polymers with chain, ring, or cross-linked
structure are obtained by linkage of several PO4
Commercial Products and Uses. The fer-
tetrahedrons via common oxygen atoms. The
tilizer industry was the largest area of ap-
18 Phosphoric Acid and Phosphates
Table 6. Stucture and nomenclature of phosphates
tetrahedra are joined exclusively by vertex shar- phates, crystalline oligomeric phosphates are
ing. uniform with regard to anion size. It is debatable
Since polyphosphates are prepared from whether crystalline, high-molecular polyphos-
acidic monophosphates by condensation, they phates are also uniform [62].
are usually referred to as condensed phosphates. The oxide ratio in metaphosphates,
Three types of condensed phosphates are distin- MIn Pn O3n , is exactly 1. Polyphosphates with
guished according to the structure of their anions very high molecular masses have practically the
[62]: polyphosphates with chain structure, cyclic same oxide ratio, and are therefore often incor-
metaphosphates, and cross-linked or ultraphos- rectly called “metaphosphates” (e.g., sodium
phates with branched chains and/or rings. hexametaphosphate for Graham’s salt). Ac-
All phosphate salts can be described as cording to the newer nomenclature, the term
combinations of oxides, e.g., Na2 H2 P2 O7 as “metaphosphate” is reserved for condensed
Na2 O · H2 O · P2 O5 . The ratio of cationic oxides phosphates with cyclic anions. So far, metaphos-
(Na2 O, CaO, H2 O) to P2 O5 is characteristic for phates are known for n = 3 – 8. There is no evi-
the individual structural types. Table 6 shows the dence for the existence of a dimeric anion with
structural relations and classifications. n = 2. Although there are indications for the oc-
The polyphosphates (MIn+2 Pn O3n+1 ) are currence of ring structures with n > 8 in some
named according to the IUPAC rules as di-, tri-, phosphate glasses, they have so far not been iso-
tetraphosphates, etc. Frequently, the older desig- lated. Cross-linked or ultraphosphates contain P
nations pyro-, tripoly-, tetrapolyphosphate, etc., atoms which are linked with each other via three
are also still used. Moreover, it is customary to O atoms. Additional designations are commonly
distinguish between chromatographically sepa- used in special cases: isometaphosphate when
rable, oligomeric phosphates with n < 12 and a ring is linked with one or more chains, and
high-molecular polyphosphates with n = 13 to isopolyphosphate if only branched chains are
> 10 000. Both glassy and crystalline forms are present. Compounds with rings linked directly
known in both groups. While mixtures of various or via chains are more specifically called ultra-
chain lengths are always present in glassy phos- phosphates. Commercially, cross-linked phos-
Phosphoric Acid and Phosphates 19
phates are not very important. So far, only a few the formation of trisodium phosphate, so that
well-defined examples of this structural type are caustic soda must be used in this step. The phos-
known. phates crystallize from the solutions as hydrates
and are separated by centrifugation. Anhydrous
salts are obtained by dehydration in rotary dry-
3.1. Sodium Monophosphates ers or directly from the solutions by spray drying
or in rotary kilns.
As a tribasic acid, monophosphoric acid Both thermal phosphoric acid and the cheaper
(orthophosphoric acid) forms three series of wet phosphoric acid are used as starting mate-
sodium salts, i.e., mono-, di-, and trisodium rials. The very pure thermal phosphoric acid is
monophosphate. Besides the anhydrous com- generally used in the production of food-grade
pounds, defined hydrates and some double salts phosphates.
are known. Table 7 lists the monophosphates
characterized in the Na2 O – P2 O5 – H2 O sys-
tem.
Monosodium dihydrogenmonophosphate
Figure 17 shows the solubility of sodium [7558-80-7], monosodium phosphate,
monophosphates as a function of temperature. NaH2 PO4 , M r 119.98, crystallizes in anhydrous
As salts of a tribasic acid whose dissociation de- form and as the mono- and dihydrates. The pH
creases greatly from the first to the third stage of a 1 % aqueous solution is 4.5. The anhydrous
( pK 1 = 2.15, pK 2 = 7.1, pK 3 = 12.4), alkali- salt decomposes upon heating from 169 ◦ C to
metal monophosphates exhibit buffer properties. 240 ◦ C, with elimination of water and formation
Sodium monophosphates are usually pro- of Na2 H2 P2 O7 .
duced by neutralization of phosphoric acid with Thermal phosphoric acid is used preferen-
soda ash or caustic soda. The latter is predom- tially for production of monosodium phosphate.
inantly used in Germany, while in the United Wet phosphoric acid is less suitable because the
States, the less expensive soda ash prevails. The impurities are only partially precipitated in the
basicity of sodium carbonate is insufficient for neutralization with soda ash or caustic soda up
20 Phosphoric Acid and Phosphates
to the first stage, so that additional recrystal- der and cream to prevent coagulation on heating.
lization would be required to purify the phos- It is also used as a component of instant desserts
phate. The dihydrate and the anhydrous salt are and puddings. Another application of Na2 HPO4
the usual commercial forms. Due to its acidity, is for silk weighting in the textile industry. Dis-
monosodium phosphate is used as phosphating odium phosphate is used as starting material for
agent for metal surface treatment and as com- the production of tetrasodium diphosphate and,
ponent of acidic detergents. Mixtures of mono- together with monosodium phosphate, for the
and disodium phosphate are used as buffers in production of higher condensed phosphates.
the pH range 5 – 8, especially in textile finishing
processes. In water conditioning, monosodium Trisodium monophosphate [7601-54-9],
phosphate is frequently added for correction of trisodium phosphate, Na3 PO4 , M r 163.95, crys-
the alkalinity of water purified by ion exchange. tallizes in the anhydrous form and with 1/2, 6,
Monosodium phosphate serves as a mineral sup- 8, or 12 H2 O. The pH of a 1 % aqueous solution
plement for feeds and as a pH stabilizer for soups is ca. 11.9. The dodecahydrate always crystal-
and juices in the food area. Monosodium phos- lizes from aqueous solutions with an excess
phate is used as raw material for the production of NaOH. Products with compositions ranging
of disodium diphosphate and higher condensed from Na3 PO4 · 12 H2 O · 14 NaOH to Na3 PO4
phosphates. · 12 H2 O · 1 /7 NaOH are obtained, depending
on the composition of the starting solution and
Disodium hydrogenmonophosphate the temperature. The stoichiometric compound
[7558-79-4], disodium phosphate, Na2 HPO4 , Na3 PO4 · 12 H2 O is unstable in aqueous solution
M r 141.97, crystallizes in the anhydrous form and can therefore only be obtained by isothermal
as well as with 2, 7, 8, and 12 H2 O. The crystal hydration of the other hydrates, which are free
structure is composed of HPO2− 4 anions in a of NaOH. Depending on composition, the do-
hexagonal close-packed arrangement, in which decahydrate dissolves at 70 – 74 ◦ C in its water
Na+ cations occupy octahedral and tetrahedral of hydration.
interstices. In addition to NaOH, several other sodium
Both thermal and purified wet phosphoric compounds such as NaOCl, NaCl, NaNO3 form
acid are used in production. Acidic phosphate double salts with trisodium phosphate [72]. Of
solution (CaHPO4 in the presence of H3 PO4 ) is these, the addition compound with sodium hypo-
treated with NaHSO4 , whereby purification oc- chlorite (chlorinated trisodium phosphate) is
curs through precipitation of gypsum [71]. Neu- commercially important.
tralization with NaOH is carried out in a second Production. Trisodium phosphate is mainly
stage. Salts are obtained from the neutralized so- produced as the dodecahydrate by complete neu-
lutions by evaporation, crystallization, and cen- tralization of phosphoric acid with caustic soda
trifugation. The desired hydrate is obtained by or soda ash and subsequent crystallization. Since
appropriate temperature control. The anhydrous neutralization with soda ash does not proceed
product is also produced by dehydration of the beyond the stage of the disodium salt, caus-
solution in a spray drying tower. Careful tem- tic soda must be added to complete the reac-
perature control is required to avoid formation tion. Frequently, mother liquors of mono- or dis-
of tetrasodium diphosphate. odium phosphate production or crystalline dis-
Anhydrous Na2 HPO4 , Na2 HPO4 · 2 H2 O, odium phosphates are used as starting materi-
and Na2 HPO4 · 12 H2 O are the commercial als. In another process, trisodium phosphate is
forms. Disodium phosphate is blended with obtained by digestion of the phosphate-rich neu-
monosodium phosphate to prepare buffer mix- tralization sludges, which accumulate in the pu-
tures. Other applications are treatment of boiler rification of wet phosphoric acid by precipita-
feedwater (see Trisodium Monophosphate page tion, with caustic soda and with addition of wa-
22), addition to detergents and cleansers, and ter glass [73]. In this process, aluminum and
preparation of mineral feedstuff supplements. In iron phosphates are converted to Fe(OH)3 and
the food industry, disodium phosphate is used Na2 Al2 SiO6 and separated from the Na3 PO4 so-
in the production of evaporated milk and other lution by filtration. On a commercial scale, it is
concentrated dairy products such as milk pow- also possible to react CaHPO4 with H2 SO4 to
Phosphoric Acid and Phosphates 21
form CaSO4 and H3 PO4 . Caustic soda can be protective layer of iron phosphate. For com-
added to the latter to give Na3 PO4 · 12 H2 O [74]. plete softening, 14 g Na3 PO4 · 12 H2 O is needed
For production of the dodecahydrate, the for 1◦ d carbonate hardness (German hardness
most widely used form, the solutions are con- scale), and 42 g for 1◦ d non-carbonate hardness
centrated. The solid salt is obtained in the form per cubic meter of water.
of flakes on cooled rollers or as powder in spray
towers. Cooling the solution gives the salt as nee- Chlorinated trisodium phosphate,
dles, which are centrifuged and dried with hot Na3 PO4 · 14 NaOCl · 11 H2 O; the pH of a 1%
air. The anhydrous salt is mostly produced from aqueous solution is ca. 11.8. The addition com-
the molten dodecahydrate by spray drying. pound of trisodium phosphate with sodium
The dodecahydrate tends to cake during hypochlorite is usually produced by the same
storage. In order to obtain a free-flowing and process as trisodium phosphate itself but with
storage-stable product it is mixed with hy- replacement of a part of the required caustic
drophilic materials such as magnesium salts or soda by NaOCl. Special processes for produc-
silicates [75]. tion of a storage-stable product are described
Uses. The most widely used commercial in the patent literature [76]. Due to its active
product is the dodecahydrate, in the form of chlorine content, chlorinated trisodium phos-
flakes, needles, or spray dried powder. The anhy- phate has bleaching and bactericidal properties
drous salt is marketed as a powder. Due to hydro- in addition to the fat- and dirt-solving effect re-
lysis, trisodium phosphate reacts strongly alka- sulting from its high alkalinity. Therefore, it is
line in aqueous media, and thus causes saponi- used as a disinfecting cleanser. The product has
fication of fats. gained considerable importance especially in
the United States where it is used in detergents
PO3− 2−
4 + H2 O HPO4 + OH
− for automatic dishwashers and in the sanitary
area. However, in Europe it is only of minor
Due to its fat- and dirt-solving properties it is importance.
used as an industrial cleansing agent for machine
parts, occupational clothing, milk cans, dishes, Sodium monofluorophosphate [10163-15-
and bottles. Trisodium phosphate is also used for 2], Na2 PO3 F, M r 144, is a white odorless pow-
surface treatment of aluminum to obtain a gloss der. Its solubility in water is 25 g per 100 g
effect. H2 O at 25 ◦ C. The NaPO3 – NaF phase diagram
Trisodium phosphate is the standard agent (Fig. 18) shows polymorphic transformations
for water softening, especially of feedwater for of Na2 PO3 F at 370 ◦ C and 410 ◦ C. The salt
steam boilers. Ions such as Ca2+ or Mg2+ re- melts congruently at 635 ◦ C; prolonged heating
act with trisodium phosphate to form water in- of Na2 PO3 F gives pyrophosphate. Hydrolysis
soluble phosphates as voluminous, sludgy pre- occurs in the presence of moist air or in solution:
cipitates, which are removed by sedimentation
Na2 PO3 F + H2 O HF + Na2 HPO4
or filtration before the purified water enters the
boiler:
Structure. The NMR spectrum of sodium
3 Ca(HCO3 )2 + 2 Na3 PO4 −→ monofluorophosphate shows that the monofluo-
Ca3 (PO4 )2 + 6 NaHCO3
rophosphate anion has the structure of the tetra-
hedral orthophosphate group in which an oxygen
atom is substituted by a fluorine atom [78].
3 MgSO4 + 2 Na3 PO4 −→ Mg3 (PO4 )2 + 3 Na2 SO4
Production. There are two main processes 3.2. Condensed Sodium Phosphates
used in the commercial production of Na2 PO3 F.
The most common process involves the Condensed sodium phosphates are formed
reaction of sodium fluoride with sodium by condensation of two or more hydro-
(meta)phosphates by melting at the eutectic genphosphate units to form chain or cyclic phos-
point [79]; the reaction is exothermic: phates, with elimination of water, usually ther-
NaF + NaPO3 Na2 PO3 F mally. For example, tetrasodium diphosphate
(commercial name, sodium pyrophosphate) is
Since the molten mixture of Na2 PO3 F, NaF, and
formed from two moles of Na2 HPO4 upon heat-
NaPO3 can react with many metals and metal ox-
ing:
ides, the choice of reactor material is important.
Platinum, platinum alloys, and glass – carbon
composites are usually used for the reactor
walls [80–82]. Other reactor materials used are
graphite [81], silver, and iron.
With oligophosphates the rate of reaction in-
creases with increasing chain length. Cyclic tri-
and tetrametaphosphates react even faster. Mad-
drell’s salt can also be used to prepare Na2 PO3 F,
as can a mixture of tetrasodium pyrophosphate The composition and structure of the prod-
and phosphorus pentoxide [80], [83]: ucts formed depend on temperature and the
Na2 O : P2 O5 ratio. Figure 19 shows the possible aqueous solution like salts of strong, monobasic
products by means of the phase diagram. acids.
In acidic solution, linear oligomers are hy- Cation-Binding Capacity. The cation-
drolyzed faster than cyclic oligomers, except for binding capacity of polyphosphates is of con-
cyclotriphosphate. For the linear phosphates, the siderable commercial importance. This term
rate gradually increases with increasing degree denotes the capability to bind cations of mul-
of polymerization. In alkaline solution, large tivalent metals, especially of Ca, Mg, and Fe,
differences are observed between the rates for and to hold them in solution such that they can
cyclic (fast hydrolysis) and linear oligomers no longer be detected with the usual precipi-
(slow). However, with increasing degree of poly- tation reagents. For example, calcium ions are
merization the differences become smaller. The not precipitated by oxalate in an aqueous solu-
first-order hydrolysis rate constants for cyclic tion containing sodium triphosphate. Numerous
and linear penta- and heptaphosphate at 50 ◦ C investigations have shown that the effect of
in 0.1 mol/L HCl are 0.128 h−1 (cyclo-P5 ), polyphosphates is not due to the formation of
0.764 h−1 (P5 ), 0.136 h−1 (cyclo-P7 ), 1.54 h−1 well-defined, soluble complexes but that they
(P7 ), and at the same temperature in 0.5 mol/L behave like soluble ion exchangers [90], [91].
NaOH: 0.0166 h−1 (cyclo-P5 ), 6.7×10−3 h−1 In aqueous solution, polyphosphates are at most
(P5 ), 7.4×10−3 h−1 (cyclo-P7 ), 0.0234 h−1 (P7 ) 30 % dissociated [92], although all OH groups
[187]. of the corresponding polyacids, apart from the
Tri- and tetrametaphosphate can be converted two terminal groups, can be titrated as strong
completely to the corresponding polyphosphates acids.
with caustic soda because the latter are compara- Bonding of the cation is primarily attributed
tively stable under these conditions. However, a to electrostatic attraction by the negatively
similar preparation of higher polyphosphates is charged polyanions. In addition, formation of
not possible because the stability of metaphos- relatively stable chelates, in which the cations
phates increases greatly with ring size, so that are bonded to several PO3 groups in the flexi-
the polyphosphates are largely decomposed be- ble polyphosphate chain, also must be assumed
fore all the metaphosphate is cleaved [62], [89]. [62]. Since multivalent cations are bound much
The hydrolytic degradation is easily moni- more strongly than the monovalent ions of alkali
tored by 31 P NMR spectroscopy or ion chro- metals, the latter can readily be exchanged for al-
matography. The 31 P NMR spectra of polyphos- kaline earth or heavy metal ions. This exchange
phates show two major peaks, with chemical and binding capacity is used for numerous pur-
shifts in the range of 5 – 10 and 15 – 20 ppm. poses to mask and inactivate interfering cations.
The high-field signal can be attributed to the end- Various methods are used to determine the
group phosphate units, and the other signal to the exchange capacity. The lime-binding capacity
middle groups [188]. The middle to end group or lime-binding value denotes the amount of
integral ratio is related to the average degree of CaO kept in solution by a specific amount of
polymerization, which decreases during hydro- alkali-metal polyphosphate in the presence of
lysis. reagents which precipitate Ca2+ . For the deter-
Ion chromatography of polyphosphate solu- mination, a predetermined amount of polyphos-
tions can be performed with an anion-exchange phate is titrated with CaCl2 in the presence of
column (Dionex AS7) and gradient elution. The sulfate ions to the onset of turbidity. Alterna-
eluent is an NaOH/NaCl solution whose con- tively, the end point is determined by forma-
tent of NaCl is increased during elution. De- tion of sparingly soluble calcium polyphosphate
tection by hydrolysis to orthophosphoric acid without addition of calcium-precipitating anions
and post-column derivatization (as molybdato- [93].
vanadatophosphate complex) has proved best The lime-binding capacity of polyphosphates
[189]. Each polyphosphate species (e.g., pen- increases with increasing chain length up to
taphosphate, hexaphosphate, etc., up to P50 ) n = 8. For higher degrees of condensation it re-
gives a peak whose integral corresponds to the mains essentially unchanged. Figure 21 shows
concentration. Hence this method allows a de- the amount of phosphate which is necessary
tailed look at the alteration of the concentration to prevent precipitation of a insoluble calcium
of distinct molecules. Figure 20 gives an exam- compound (e.g., calcium oxalate) as a func-
ple for a highly condensed polyphosphate.
Phosphoric Acid and Phosphates 25
Figure 20. Ion chromatograph of a highly condensed polyphosphate Na(PO3 )n with a P2 O5 content of 68 % [190]
tion of chain length. The lime-binding capac- phates themselves exhibit no colloidal proper-
ity is also dependent on concentration, pH, tem- ties in pure, aqueous solution. Essentially, the
perature, and the presence of electrolytes [94]. effect is due to adsorption of multiply charged
In contrast to polyphosphates, cyclic metaphos- polyphosphate anions on suspended or emulsi-
phates exhibit only minor exchange capability fied particles, electrical charging of the latter,
toward multivalent cations. and consequent change of the physicochemical
characteristics [95].
The dispersive action of polyphosphates is
one of the most prominent effects. Viscosity re-
duction, which always occurs concurrently, is
directly related to this effect. For instance, stiff,
tenacious pastes such as blanc-fixe (BaSO4 )
can be converted to stable, free-flowing suspen-
sions by addition of small amounts of Graham’s
salt. Kaolin suspensions of high solids content
and low viscosity can be prepared with small
amounts of polyphosphate.
The improvement of the soil antiredeposition
capacity in the laundry process by polyphos-
phates can also be regarded as suspension sta-
Figure 21. Lime-binding capacity of polyphosphates as a bilization. Although polyphosphates themselves
function of chain length are not surface-active and thus are not really
The figure shows the amount of polyphosphate which is
necessary to complex all calcium ions in 10 L of water with
emulsifiers, they increase the surface activity of
a hardness of 10◦ dH wetting agents. Presumably, the effect is due to
a dispersion of the surface-active substances.
The peptization of proteins is another col-
Colloidal Behavior. Many applications of loid chemical effect. It plays an important role
polyphosphates are based on colloidal effects. in the production of processed cheese and in
These are secondary effects because polyphos-
26 Phosphoric Acid and Phosphates
meat processing. Protein is partially digested by so-called “return” process. The crystal slurry ob-
polyphosphate and converted to a sol. tained by evaporation is combined with recycled
In many cases the dispersing effect of material in a twin screw and charged to a rotary
polyphosphates is due to adsorption and is sup- dryer [99].
plemented by stabilization due to elimination of In another process, NaH2 PO4 solu-
interfering factors (calcium binding). tion is spray dried at 140 – 195 ◦ C, giving
10 – 40 % Na2 H2 P2 O7 . Subsequent calcination
at 200 – 220 ◦ C gives pure Na2 H2 P2 O7 [100].
3.2.2. Sodium Diphosphates Disodium diphosphate is used as a (tropically
stable) acid carrier in baking powder, for im-
The following sodium diphosphates (pyrophos- provement of flow properties in flour, for pH
phates) are known as crystalline compounds regulation, and in dental care products for pre-
[96]: vention of tartar formation.
NaH3 P2 O7 Na3 HP2 O7 · H2 O
Na2 H2 P2 O7 Na3 HP2 O7 · 9 H2 O Tetrasodium diphosphate [7722-88-5],
Na2 H2 P2 O7 · 6 H2 O Na4 P2 O7
Na3 HP2 O7 Na4 P2 O7 · 10 H2 O
tetrasodium pyrophosphate, neutral sodium py-
rophosphate, Na4 P2 O7 , M r 265.91, d 2.50,
mp 985 ◦ C. Its solubility in water is 5 g
Of these, only disodium diphosphate and Na4 P2 O7 /100 g H2 O at 20 ◦ C and 35 g at 80 ◦ C.
tetrasodium diphosphate are produced on a large The pH of a 1 % aqueous solution is 10.4. The
scale. usual commercial product is the anhydrous salt
in the form of a white, nonhygroscopic powder.
Disodium dihydrogendiphosphate However, in contact with moist substances it acts
[7758-16-9], disodium diphosphate, acidic as a drying agent with formation of Na4 P2 O7
sodium pyrophosphate, Na2 H2 P2 O7 , M r · 10 H2 O.
221.97, d 2.31. Its solubility in water is 13 g The decahydrate, Na4 P2 O7 · 10 H2 O, d 1.83,
Na2 H2 P2 O7 /100 g H2 O at 20 ◦ C, and 20 g at mp 79.5 ◦ C (with loss of H2 O), is also marketed
80 ◦ C. The pH of a 1 % aqueous solution is but on a much smaller scale. It crystallizes from
4.1. The usual commercial product is the an- aqueous solution below the melting point. Anhy-
hydrous, nonhygroscopic salt in powder form. drous Na4 P2 O7 is known in five different mod-
The hexahydrate, Na2 H2 P2 O7 · 6 H2 O, d 1.85, ifications with transition temperatures between
crystallizes from aqueous solution below 27 ◦ C. 400 and 545 ◦ C. Only the low-temperature form
Above this temperature, it is converted to the is stable below 400 ◦ C.
anhydrous form. Tetrasodium diphosphate is produced by
Disodium dihydrogendiphosphate is pro- calcination of disodium hydrogenphosphate at
duced from sodium dihydrogenmonophosphate 300 – 900 ◦ C:
by heating at 200 – 250 ◦ C:
2 NaH2 PO4 −→ Na2 H2 P2 O7 + H2 O 2 Na2 HPO4 −→ Na4 P2 O7 + H2 O
Careful control of reaction temperature and time In the two-stage process, a concentrated
is required to achieve complete conversion of monophosphate solution is dehydrated to give
the monophosphate and to avoid formation of anhydrous disodium hydrogenphosphate in a
higher condensed phosphates. Reaction times of spray drying tower and subsequently condensed
1 – 6 h at 215 – 245 ◦ C are used [97]. The degree to diphosphate in a rotary kiln. For improvement
of condensation can be influenced by regulating of the heat economics, the hot off-gases from the
the partial pressure of water vapor [98]. second stage can be used for spray drying. In an-
Usually, monophosphate is converted to other process, phosphoric acid and caustic soda
diphosphate continuously in rotary kilns. are metered separately into a spray drying tower
Smaller plants also use batch processes with in order to utilize the heat of neutralization [101].
plate dryers or electrically heated pans. Both rotary kilns and spray drying towers are
A monophosphate solution made from phos- used in the single-stage production of Na4 P2 O7 .
phoric acid and caustic soda in situ is used in the In the rotary kiln process, the phosphate solution
Phosphoric Acid and Phosphates 27
is sprayed onto a bed of already formed, solid modification than from the LT form. The anhy-
monophosphate (return process). A single-stage drous modifications are more soluble than the
spray tower process is described below (see Pen- hexahydrate. Therefore, on dissolution a con-
tasodium Triphosphate page 28). Generally, the centration of ca. 32 % Na5 P3 O10 is attained ini-
processes for production of sodium triphosphate tially which is considerably higher than that of
can also be used for sodium diphosphate. a solution in equilibrium with the hexahydrate
Tetrasodium diphosphate is used in deter- (ca. 13 % Na5 P3 O10 ). This occurs especially on
gents and cleansers, in metal surface treatment, dissolution of the LT form, from which the hexa-
and in oil well drilling fluids for viscosity ad- hydrate is formed at a slower rate.
justment. In the food area, Na4 P2 O7 is used as On heating to 100 – 120 ◦ C, the hexahydrate
a component of cold puddings and ice cream hydrolyzes to give mono- and diphosphate:
for regulating the consistency. The stabiliza-
tion of toothpastes based on calcium hydro- Na5 P3 O10 · 6 H2 O −→ Na3 HP2 O7 + Na2 HPO4 + 5 H2 O
genphosphate is another important application.
Na3 HP2 O7 + Na2 HPO4 −→ Na4 P2 O7 + NaH2 PO4
phosphoric acid with caustic soda or soda ash, In the FMC process, the monophosphate so-
is used as starting material. Both single-stage lution is sprayed upwards from nozzles at the
and two-stage processes are used for dehydra- bottom of the tower [112]. The particles move
tion of the solution and subsequent condensation upward to the flame zone at the top of the tower
to triphosphate. and are then carried downward with the hot gas
In the two-stage processes (Fig. 22), the so- stream.
lution is dehydrated in the first stage to give an Single-stage rotary kiln processes are carried
anhydrous monophosphate mixture. Frequently, out both according to the cocurrent and counter-
partial condensation with formation of diphos- current principle. The monophosphate solution
phate already occurs in this stage. The actual is sprayed through a flame directed into the ro-
condensation to triphosphate then follows in the tary kiln and onto a hot bed of previously cal-
second stage. cined material [113]. The product then moves
Generally, spray dryers are used for dehydra- cocurrently with the hot combustion gases to the
tion of the monophosphates, and rotary kilns for discharge port and thus is posttempered at a re-
the conversion to triphosphate. The required en- duced temperature. Advantages of this mode of
ergy is supplied by hot gases from a combustion operation are the avoidance of caking and the
chamber or by an oil or gas flame in the rotary possibility to produce a product with a high con-
kiln. tent of the LT form. The high energy consump-
A fluidized-bed reactor has also been recom- tion is, however, a disadvantage.
mended for the conversion of dried monophos- A countercurrent rotary kiln process is de-
phates to triphosphate [107]. In another process scribed by FMC [114]. The material is conveyed
rotary kilns are used in both stages, and a gran- countercurrently to the heating gases, which are
ular end product is obtained by grinding the in- generated in a combustion chamber outside of
termediate product and adding water before cal- the rotary kiln. This process permits a substan-
cination [108]. tially better heat utilization than the cocurrent
In the single-stage process, rotary kilns or process. However, the frequent occurrence of
spray drying towers are used. In the Hoechst- caking at the charging point is a disadvantage.
Knapsack process (Fig. 23), the monophosphate Numerous suggestions for modification of
solution is sprayed at 1 – 2 MPa [109] into a the commercial processes are found in the patent
stainless-steel spray tower [110]. Burners, ar- literature. They are aimed at the preparation of
ranged concentrically around the nozzle, gener- pentasodium phosphate with special application
ate a flame zone directed conically towards the properties and concern especially production of
center of the tower. The sprayed solution moves the low-temperature modification [115], [116],
downward cocurrent with the burner gases and attainment of low bulk densities [117], and in-
is rapidly dehydrated and converted to triphos- crease of abrasion resistance [118]. Partially hy-
phate. Most of the Na5 P3 O10 is collected in the drated products are prepared for improvement
tower cone and discharged. Finer particles are of the solubility characteristics [119], [120].
separated from the off-gas by cyclones. The off- Sodium triphosphate hexahydrate is pro-
gas is then further purified by a liquid washing. duced by hydration of anhydrous Na5 P3 O10 .
Free-flowing, powdery products are ob- It is important that too high a temperature rise
tained, with triphosphate contents of up to 98 %. is avoided in the exothermic hydration reac-
The ratio of LT/HT form can be varied over a tion because the triphosphate anion is cleaved
wide range by controlling the temperature and hydrolytically by the water of hydration at ele-
the water content in the gas phase. Moreover, vated temperatures. In the Hoechst-Knapsack
a particular crystalline form can be obtained by process an excess of water is sprayed onto
simultaneously spraying seed crystals of the de- Na5 P3 O10 in a rotary kiln. The excess water
sired modification [111]. Coarse Na5 P3 O10 par- is evaporated by simultaneously blowing air
ticles (> 0.15 mm) can also be prepared by this over the product, dissipating part of the heat
seed crystal method. The required crystallites of hydration and maintaining the product tem-
are taken from the residues of the dust filter bag perature at 60 – 70 ◦ C [121]. In the Monsanto
because these flue dusts have favorable spray process crushed ice is used for the hydration of
and suspension characteristics. Na5 P3 O10 to the hexahydrate [122].
Phosphoric Acid and Phosphates 29
Figure 24. Condensed phosphates which can be prepared from NaH2 PO4 by heating and their interrelationship [62]
Upon tempering, the glassy Graham’s salt is glassy clods, which are subsequently broken and
converted to crystalline, high-molecular forms ground.
(Kurrol’s and Maddrell’s salt) or to cyclic In another process, fused phosphates are
sodium trimetaphosphate, Na3 P3 O9 . Figure 24 obtained directly from elemental phosphorus
shows the various condensed phosphates which [123]. Phosphorus and caustic soda are sprayed
can be obtained from NaH2 PO4 and their con- by air into a spray tower lined with graphite
ditions of preparation [62]. bricks. Molten polyphosphate is formed in the
phosphorus flame at 1500 – 1800 ◦ C, accumu-
Fused phosphates (glassy polyphosphates), lates at the tower bottom, and runs onto a cooled
Nan+2 Pn O3n+1 , are all hygroscopic and wa- drum. About 30 % of the combusted phosphorus
ter soluble. The pH depends on the degree of is entrained by the off-gas in the form of fused
condensation. In 1 % aqueous solutions it ranges phosphate and small amounts of P4 O10 . These
from 8.4 for hexasodium tetraphosphate to 4.0 are converted to an aqueous solution of sodium
for long-chain polyphosphates (n > 20). phosphate in a downstream wash tower and re-
High-molecular fused phosphates are pro- turned to the combustion tower. The energy
duced from acidic monophosphates in tank fur- required for dehydration of caustic soda and
naces lined with zircon mineral bricks (Fig. 25). wash solution as well as for production of the
The average chain length depends on tempera- polyphosphate melt is supplied entirely by the
ture, duration of fusion, and water vapor pres- heat of phosphorus combustion.
sure of the melt. The melt temperatures are A posttreatment of the ground products by
600 – 800 ◦ C, depending on the Na2 O : P2 O5 addition of Na2 CO3 or Na4 P2 O7 or by spray
ratio. The outflowing melt is chilled on water- coating with alkaline solutions is recommended
cooled barrels or drums with formation of for decreasing the hygroscopicity [124].
Phosphoric Acid and Phosphates 31
addition to the feedwater, they initially keep the sodium tripolyphosphate (STPP), is by far
hardeners in solution. The hydrolytic degrada- the most important product. Many indus-
tion to monophosphates occurs only at elevated trial cleansers contain 20 – 35 % pentasodium
temperature in the boiler. Thus, the hardeners triphosphate as builder. On a much smaller scale,
are precipitated there and can be discharged as tetrasodium diphosphate is also used for these
sludge. applications but its significance has declined
Another property of polyphosphates impor- steadily since the 1970s. The higher condensed
tant in practice is their capability, even at very fused phosphates are also used, i.e., in specialty
low concentrations, to prevent precipation of cleansers and personal hygiene preparations.
calcium carbonate. This effect is utilized in the Triphosphate performs several functions in
phosphate threshold treatment of tap water, e.g., the laundry process. Primarily, it softens the wa-
in communal water conduits, in warm water ter by masking alkaline earth metal ions and pre-
facilities, or in industrial cooling water sys- venting their deposition on the fabric. In addi-
tems. The required amounts of phosphate, usu- tion, triphosphate prevents precipitation in the
ally 2 – 5 g/m3 of water, are much lower than the washing machine, especially on the heating ele-
amount necessary for complexation of the hard- ments [135]. Furthermore, the pronounced dis-
eners. In this way, the precipitation of calcium persing capacity of triphosphate and its emul-
carbonate can be completely prevented at mod- sion stabilizing effect are important in the laun-
erate temperatures and water hardnesses and dry process. Condensed phosphates increase the
normal pH values. At elevated temperatures and surface activity of wash active substances and
higher water hardnesses, crystal growth is hin- thus their detergency (synergistic effect).
dered to such an extent that no firmly adhering To an increasing extent, Na5 P3 O10 is also
deposits can be formed. It is assumed that growth used in automatic dishwasher detergents, which
of the crystal nuclei is stopped or strongly re- contain 20 – 50 % pentasodium triphosphate. In
tarded by adsorption of polyphosphate anions this application, the triphosphate is used es-
[133], [134]. pecially for its water softening and dispersing
It is important in the threshold process that properties and for its advantageous pH range
the phosphate concentration does not exceed [136].
a certain limit because otherwise precipitation
of sparingly soluble phosphates begins. These Food Industry. The versatile applicability
can only be redissolved at substantially higher of condensed phosphates in the production and
concentration by complexation. Water-soluble, processing of food is essentially due to their ion-
mostly long-chain fused phosphates such as Gra- exchange and colloid properties.
ham’s salt are used in large waterworks. They In the production of processed cheese, con-
are added to the water carrying system as a densed phosphates are used as rectifying or melt
2 – 5 % solution. Slow-dissolving, glassy cal- salts. In the production process, calcium ca-
cium sodium polyphosphates are used mostly seinate is converted by sodium polyphosphates
in smaller works and in private residences. They to sodium caseinate and is peptized. A stable
are charged in form of lumps to a lock installed suspension is formed from this product together
in the main line or in a bypass, where they dis- with milk fat, finely dispersed during melting,
solve slowly in the passing water [95]. and the substances dissolved in the aqueous
An additional advantage of the phosphate phase. Polyphosphates of medium chain length
threshold treatment is the anticorrosion effect are preferred for this application. An impor-
due to the formation of a firmly adhering, dense, tant application of long-chain polyphosphates
protective layer of iron calcium phosphate. is their bacteriostatic effect in cheese products.
Phosphates also act as corrosion inhibitors for To a small extent, mono- and diphosphates are
copper, zinc, and aluminum. added as corrective and buffer salts [95].
Polyphosphates are also used in the produc-
Detergents and cleansers (→ Cleansing tion of concentrated milk products such as evap-
Agents ; → Laundry Detergents) are major orated milk and milk powder, especially to pre-
applications of polyphosphates. Pentasodium vent aggregation of the casein (heat coagulation)
triphosphate, mostly marketed under the name by deactivation of calcium ions.
Phosphoric Acid and Phosphates 33
Furthermore, the dispersing and calcium- During the soaking of hides and skins, they pre-
binding properties of polyphosphates are uti- vent coagulation of blood and reduce the hard-
lized in the preparation of instant puddings, ness of the water. In the liming step, the prop-
ice cream, skimmed milk products, and instant erties of a dispersing agent are necessary. The
sauces. In end-products, they act as stabilizers polyanions stabilize the lime slurry in the state of
for batters and as gelation regulators. single solid particles, which are able to penetrate
Polyphosphates are used for prevention of quicker. The result is a short and effective liming
blood coagulation in the preparation of blood step. Another important function is the reaction
plasma from the blood of slaughtered animals with protein chains in the skin. It is compara-
in the Fibrisol process. ble with a mild tanning process, so polyphos-
Polyphosphates effect disaggregation and phates are used as pretanning agents [95]. These
peptization of muscular albumin. Thus, they functions are important in the commonly used
act similarly to natural adenosine triphosphate, tannage with chromium salts and in classical
which is present in living organisms but not in vegetable tannage. In the latter process the iron-
meat. This effect of polyphosphates, especially binding capacity is also essential, because the
of diphosphates, is utilized in the preparation of complexation of iron ions by polyphosphates
cooked sausage and boiled, cured meats to avoid prevents the formation of iron stains. During the
loss of quality due to a change in the protein complete beamhouse work, many washing steps
structure and the resulting loss of tissue water. are necessary. Addition of polyphosphates to the
water prevents the formation of lime stains or
Baking Aids. Disodium dihydrogendiphos- lime shadows by complexing Ca ions.
phate is widely used as an acid carrier in bak-
ing powders, especially in Europe. At moder- Paint Industry. In the production of paints,
ate temperatures it does not react with NaHCO3 especially emulsion paints, the main compo-
contained in baking powder and thus permits nents water, pigments, fillers, and binder are
the preparation or storage of large amounts stirred together to form a paint with good ap-
of dough. The acidic diphosphate reacts with plication properties. Manufacturers aim for high
sodium hydrogencarbonate only during the bak- solids contents to give good covering power and
ing process with evolution of carbon dioxide for good storage stability of the paint. Both goals
and formation of tasteless disodium monophos- can be achieved by adding dispersing agents to
phate. In the United States, Na2 H2 P2 O7 is the water in the first production step. Polyphos-
used only for fine baked products; otherwise phates are well-known dispersing agents. Com-
monocalcium phosphate, Ca(H2 PO4 )2 · H2 O, is parative tests show that Polyphosphates with
used predominantly. Because of its high reactiv- chain lengths between n = 6 and n = 10 give the
ity towards sodium hydrogencarbonate, mono- best results. The dispersing effect is due to ad-
calcium phosphate is often mixed with sodium sorption of anionic phosphate molecules on the
aluminum sulfate, NaAl(SO4 )2 , which reacts surface of the pigments and fillers, which elimi-
only at baking temperature. In addition, it is nates the attractive forces between the particles
added to flour as “bread improver” in bread bak- [191]. In current emulsion paint formulations,
ing [137]. a combination of polyphosphates and polyacry-
Sodium aluminum phosphates of com- lates is used, because in addition to optimal dis-
position NaH14 Al3 (PO4 )8 · 4 H2 O and persing and storage results advantages in scrub-
Na3 H15 Al2 (PO4 )8 are now used in the United bing resistance can be obtained.
States as acid carriers in baking powders [137].
They are less reactive than monocalcium phos- Construction Industry. Short-chain
phate and develop their full effect as expanding polyphosphates, especially the di- and triphos-
agents only at baking heat. This is advantageous phates, are used as setting retarders for con-
especially for the durability of prefinished mix- crete and cement-based mortar. Addition of
tures. combinations of tartraric or citric acid with
long-chain polyphosphates to gypsum plaster
Leather Industry. In the production of results in optimum workability and plasticity. In
leather, polyphosphates act in various ways. cement-based self-levelling floor compounds,
34 Phosphoric Acid and Phosphates
cheaper potassium chloride is also used instead 448.43, mp 614.5 ◦ C (decomp.), crystallizes in
of KOH [138]. Various methods have been sug- the anhydrous form and as the dihydrate. The an-
gested for quantitative removal of the hydrogen hydrous salt is strongly hygroscopic. Its solubil-
chloride formed: use of ion exchangers [139], ity in water is ca. 200 g/100 g H2 O at 20 ◦ C. The
long-chain tertiary amines [140], or distillation pH of a 1 % aqueous solution is 11.5. Like the
with octane [141]. The economics depend on the corresponding sodium compound, pentapotas-
possibility of using the hydrogen chloride. sium triphosphate is produced from 2 mol of
Uses. The potassium phosphates KH2 PO4 K2 HPO4 and 1 mol of KH2 PO4 . It is used as a
and K2 HPO4 are used in the food area for builder in liquid detergents.
mineral enrichment of fruit juices and as sta-
bilizers in milk products. Potassium dihy- Kurrol’s salt [29057-10-1], (high-molecu-
drogenphosphate is used as a nutrient salt lar potassium polyphosphate) (KPO3 )x , M r
for mushrooms and cormophytes. Crystals of (118.09)x , where x can vary from 400 to 20 000
KH2 PO4 are used as piezoelectric vibrators depending on the conditions of preparation, d
[142]. Dipotassium phosphate is suitable as a 2.26, mp 813 ◦ C. Although it is a true polyphos-
buffer in the range pH 9, e.g., for pH adjustment phate with chain structure, the incorrect designa-
of water – glycol mixtures in cooling systems of tion potassium metaphosphate is frequently still
automotive engines in order to avoid corrosion found in the literature. Kurrol’s salt is insoluble
[143]. Mono- and dipotassium phosphate are in pure water. However, in the presence of other
further processed to potassium polyphosphates. alkali-metal ions, especially Na+ , it dissolves to
form a viscous gel.
Tetrapotassium diphosphate [7320-34-5], Kurrol’s salt is generally produced by heat-
tetrapotassium pyrophosphate, K4 P2 O7 , M r ing KH2 PO4 at 350 – 500 ◦ C in a rotary kiln. In
330.35, crystallizes in the anhydrous form and another process, (KPO3 )x is produced as a spray
the mono- and trihydrates. The anhydrous salt dried product from aqueous KH2 PO4 solution in
and the monohydrate are strongly hygroscopic. a hot gas stream at 330 – 390 ◦ C [144]. Due to
The solubility of K4 P2 O7 in water is 187 g/100 g its good dispersing action, Kurrol’s salt is used
H2 O at 25 ◦ C, and the pH of a 1 % aqueous so- as an additive in soaps and cleansing agents.
lution is 10.3.
Tetrapotassium diphosphate is produced
by the same methods as the corresponding 3.3.2. Ammonium Phosphates
sodium salt, i.e., by dehydration of K2 HPO4
at 350 – 460 ◦ C. Like the other alkali-metal The most important application of ammonium
polyphosphates, K4 P2 O7 also has pronounced phosphates is as fertilizers (→ Phosphate Fertil-
dispersive properties as well as the capac- izers). Other applications are known, especially
ity to bind multivalent cations and to keep as flame retardants.
them in solution. Despite the higher price, The following crystalline monophosphates
tetrapotassium diphosphate is used preferen- exist in the NH3 – P2 O5 – H2 O system [145]:
tially as builder in liquid detergent formulations
containing 20 – 25 % diphosphate and ca. 50 % NH4 H2 PO4 (NH4 )2 HPO4
NH4 H2 PO4 · H3 PO4 (NH4 )3 PO4 · 3 H2 O
water in addition to wash active substances. The NH4 H2 PO4 · H3 PO4 · H2 O (NH4 )3 PO4 · 2 (NH4 )2 HPO4
reasons are the substantially higher water solu-
bility compared with the sodium salts and the
hydrolytic stability of the diphosphate anion. Only the mono- and diammonium phosphates
Potassium diphosphate is also used as a sta- are commercially important. The compound
bilizer in foods and for the prevention of tartar (NH4 )3 PO4 and the double salt (NH4 )3 PO4
formation. Use as a catalyst in the production of · 2 (NH4 )2 HPO4 are unstable at room tempera-
Buna is mentioned in some product information ture. They decompose with release of ammonia
brochures. and formation of (NH4 )2 HPO4 .
aqueous solution succeeds only in the pres- of an aqueous phase with increased P2 O5 con-
ence of excess phosphoric acid [157]. Adher- tent. However, its solubility is low (220 mg/L
ing phosphoric acid gives hygroscopic products CaO and 530 mg/L P2 O5 at 25 ◦ C).
which tend to decompose further by absorption The dihydrate is produced by neutralization
of atmospheric moisture. Therefore, commercial of phosphoric acid with calcium hydroxide,
products are made with an excess of CaO and with cooling to avoid formation of anhydrous
contain up to 20 % calcium hydrogenphosphate. CaHPO4 . Thermal phosphoric acid is used as
Monocalcium phosphate is produced by neu- starting material in the production of CaHPO4
tralization of phosphoric acid with calcium · 2 H2 O for use in toothpastes. However, feed-
oxide or hydroxide [158]. Only thermal phos- stuff phosphates are produced predominantly
phoric acid is used for production of food-grade from defluorinated wet phosphoric acid.
quality (e.g., for baking aids). Defluorinated wet For defluorination, the acid is partially neu-
phosphoric acid is used mostly for feed phos- tralized with calcium hydroxide or carbonate.
phate. The starting materials are reacted in ves- The fluoride precipitates as calcium hexafluoro-
sels made of stainless steel by means of high- silicate together with phosphates of bi- or multi-
intensity agitators or in continuously operating valent metal ions such as Fe and Al. The P2 O5 -
mixers. Some of the water is evaporated by the containing precipitate is filtered and used for fer-
heat of reaction. A pulpy to crumbly product tilizer production. Na2 SiF6 or K2 SiF6 can also
is obtained, which is subsequently dried and be precipitated by addition of sodium or potas-
ground. sium salts. After subsequent addition of calcium
Products with low bulk density are obtained hydroxide, the precipitated CaHPO4 · 2 H2 O is
from a slurry of the starting components by spray filtered, dried, and ground.
drying with hot air. Predominantly monohydrate For a large decrease of the fluoride content,
is produced by these processes because the an- an additional defluorination can be carried out
hydrous salt is less stable towards atmospheric by adding SiO2 in the form of bentonite [159].
moisture. In a more recent process, stoichiometric
A relatively water-stable, less reactive prod- quantities of CaCl2 , NaOH, and H3 PO4 are
uct is obtained by addition of small amounts of added simultaneously to an intensively agitated
various metal salts, e.g., of potassium or alu- reactor [160]. In a variation of this process,
minum [132]. CaCl2 and NaOH are partially replaced by an
The anhydrous salt is formed by carrying out aqueous suspension of calcium carbonate [161].
the reaction at 140 ◦ C. In a posttreatment step at The water-adsorptive capacity of CaHPO4
200 – 220 ◦ C, the crystals become coated with a · 2 H2 O also has a function in its application
glassy, essentially water-stable, protective layer as a polishing compound in toothpastes. Highly
(anhydrous coated calcium phosphate, ACCP). adsorptive products can be prepared by adding
In the United States, monocalcium phosphate H3 PO4 to a suspension of CaCO3 and homoge-
is used mainly as a leavening aid in the produc- nizing the reaction mixture at the drip spot with
tion of self-raising flour. Further applications are a disperser [162].
in mineral enrichment of foods, as a stabilizer The anhydrous salt is produced by the same
for milk products, and as a feedstuff additive in processes as are used for the dihydrate, but pre-
place of calcium hydrogenphosphate. cipitation is carried out above 80 ◦ C. Calcium
hydrogenphosphate, in the form of its dihydrate
Calcium hydrogenphosphate [7757-93-9], and sometimes also as anhydrous salt, is used as
dicalcium phosphate, CaHPO4 , M r 136.06, a mineral supplement in feedstuff. The dihydrate
crystallizes in the anhydrous form, d 2.89, tri- is used as a component of toothpastes because
clinic, and as the dihydrate, d 2.32, monoclinic. of its advantageous polishing properties and low
The dihydrate is slowly converted to the anhy- abrasiveness [163]. Stabilizers such as MgCl2 ,
drous salt at 36 ◦ C (incongruent melting point). Mg3 (PO4 )2 , MgHPO4 · 2 H2 O, or Na4 P2 O7 are
Substantially higher temperatures are required added to prevent hardening of toothpastes pre-
for production of the anhydrous salt. CaHPO4 pared with CaHPO4 due to dehydration during
· 2 H2 O dissolves in water with precipitation of storage.
hydroxyapatite, Ca5 (PO4 )3 OH, and formation
Phosphoric Acid and Phosphates 39
Aluminum polyphosphate, [Al(PO3 )3 ]n , is Table 9. Phosphate demand for the food, beverage, and baking in-
insoluble in water and acids. Upon heating at dustry (in 103 t P2 O5 ) ∗
900 – 1000 ◦ C it is converted to a cyclic tetram- Region 1988 1990 1992 1994 1996 ∗∗
etaphosphate with mp 1230 –1250 ◦ C [171]. Europe 27 28 29 35 40
Aluminum polyphosphate is produced from America 78 80 82 95 96
monoaluminum phosphate by heating at 600 ◦ C. Asia 6 7 8 10 11
It is used in the enamel industry in heat-resistant World 120 125 130 145 150
glasses and as component of optical glasses. ∗Main phosphates: STPP, SHMP, TSP, SAPP, SAlP, MCP,
Aluminum polyphosphates with a molar ratio DSP (without H3 PO4 ). ∗∗ Estimated.
MSP monosodium phosphate ∗Main phosphates: Glassy phosphates, SHMP, STPP, TSPP,
MSP, DSP. ∗∗ Estimated.
DSP disodium phosphate
TSP trisodium phosphate
TSPP tetrasodium pyrophosphate
Phosphoric Acid and Phosphates 41
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