ICH 305

1. Manufacture of wet-process phosphoric acid

In recent years and at present, rapid expansion in the

manufacture of wet-process phosphoric acid (H3PO4) has resulted
from the increased demand for high-analysis fertilizer, triple
superphosphate, and ammonium and dicalcium phosphates. H3PO4 is
prepared by the action of sulphuric acid (H2SO4) on ground
phosphate rock. The equipment is lined with lead, stainless steel, or
acid proof brick, and sufficient time provided in the various agitation
for the reaction to go to completion. The temperature in the digester
should be kept low enough to ensure the precipitation of gypsum
(CaSO4.2H2O), and not anhydrite (CaSO4). If the latter is formed, it
subsequently hydrates and causes plugging of pipes. Acid made by
this process is used almost entirely in fertilizer production, where
impurities are not important, or after some purification for various
sodium phosphates.
The essential reaction for the dihydrate process is:
CaF2.3Ca3 (PO4)2 + 10H2SO4 + 20H2O 10CaSO4.2H2O(8) + 2HF
+ 6H3PO4
or more simply expressed,
Ca3(PO4)2 + 3H2SO4 + 6H2O 2H3PO4 + 3CaSO4. 2H2O
Often, wet-process acid is concentrated, but care must be taken to
delay fouling of the tubes and reduce down time for cleaning, as, for
example, by the use of forced circulation.
A2. Acidulation with hydrochloric acid to produce phosphoric
acid
This method of acidulating rock phosphate with hydrochloric
acid (HCl) is known as the Haifa process. This process uses
hydrochloric acid instead of sulphuric acid employed in the dihydrate
process. The calcium chloride is soluble in phosphoric acid rather
than being precipitated as gypsum (CaSO4.2H2O), when H2SO4 is
used.
This method of using HCl was first developed by the Israeli
Mining Industries (IMI) and has operated a demonstration plant in
Haifa since 1962. The Haifa process has the advantage of utilizing
waste or by-product HCl.
Apart from calcium chloride, other soluble by-products include
fluorine compounds and some impurities. The success of the Haifa
process lies in the ability to separate H3PO4 from the highly soluble
CaCl2. After the removal of the solid impurities, the solution is
contacted with butyl alcohol or isoamyl alcohol to selectively extract
the H3PO4 and HCl, leaving the CaCl2 in the aqueous layer which is
treated as a waste. Thereafter, the acids enter the aqueous phase
upon contact with demineralized water and separate as a solution of
P2O5 and HCl. The mixture is then concentrated to H3PO4, and HCl in
the exhaust vapour from the concentrator is recycled to the system.
If the phosphate rock contains fluoride, hydrofluoric acid (HF),
is either removed from the acid aqueous mixture before solvent
 extraction, or extracted into the solvent alongside the excess HCl and
accompanies the latter when it is being separated from the H3PO4.
The main reaction in the Haifa process involving phosphorite, is given
below:
CaF2 . 3Ca3 (PO4)2 + 20HCl 10 CaCl2 + 6H3PO4 + 2HF (1)
A flow chart for the Haifa process is illustrated in Fig. 1 below:

HCl Phosphate Rock

Digestion

Removal of solid
impurities

HCl, solvent

Solvent Extraction

Washing solvent Separation

HCl, solvent
and CaCl2
Distillation and
Evaporation
H2O + HCl
CaCl2
H3PO4
Fig. 1. Flow chart for production of H3PO4 by the Haifa process
3. Manufacture of phosphorus and purified derivations
Phosphorus is produced by the electric-furnace method. The
following reaction is considered to take place, the raw materials
being phosphate rock, silica, and coke:
CaF2 . 3Ca3 (PO4)2 + 10SiO2 + 15C 10CaSiO3 + 6P + 15CO + SiF4
or more simply expressed,
2Ca3 (PO4)2 + 6SiO2 + 10C 6CaSiO3 + P4 + 10CO
The silica is an essential raw material which serves as an acid
and a flux. About 20% of the fluorine present in the phosphate rock
is converted to SiF4 and volatilized. In the presence of water vapour,
this reacts to give SiO2 and H2SiF6.
3SiF4 + 2H2O 2H2SiF6 + SiO2
The CO produced is employed as a fuel in preparing the
furnace charge (agglomeration). The slag removed from the furnace
is sold as ballast, or aggregate or fill. Ferrophosphorus is tapped as
necessary, its quality being dependent on the amount of iron
originally in the burden or added to it. The phosphorus is employed
usually as an intermediate product, burnt or oxidized to P2O5 which is
dissolved in water to form acids, or other compounds.
The electric-furnace process permits the use of lower grade
rock than the wet-process, since the slag carries off most of the
impurities. The principal requirement is cheap electricity. The rock
must be charged in lump form or as +8 mesh. Fine material tends to
block the exit of the phosphorus vapours which causes bridging and
 uneven descent of the furnace charge, resulting in puffs and the
carrying over of excessive quantities of dust.

4. H3PO4 from Phosphorus

An increasing quantity of pure, strong H3PO4 is manufactured
from elemental phosphorus by oxidation and hydration:
4P + 5O2 2P2O5 (oxidation)
P2O5 + 3H2O 2H3PO4 (hydration)
The oxidation tower or chamber, is made of acid-resistant brick
or stainless steel. H3PO4 runs down the walls and absorbs about 75%
of the P2O5 and also provides the needed heat for the reaction(s).
This acid is cooled, some drawn off, and some recirculated. The
remaining 25%, as a mist is passed to a Cottrell or Brink mist
eliminators for collection. Some modern plants produce
superphosphoric acid, 76% P2O5, equivalent to 105%
orthophosphoric acid, with which higher-percentage plant foods can
be made e.g ammonium polyphosphate, 54% superphosphate. Other
plants produce 75 to 85% orthophosphoric acid, depending on the
process for which it is to be used.

5. Sodium Phosphates
The various sodium phosphates represent the largest quantity
of chemicals based on pure H3PO4 obtained mostly from elemental
phosphorus. Orthophosphates are based on the simple PO 4
tetrahedron as a monomeric unit and include monosodium
 phosphate, NaH2PO4 (MSP); disodium phosphate, Na2HPO4 (DSP),
and trisodium phosphate, Na3PO4.¼NaOH.12H2O, (TSP). The first
two sodium salts (MSP and DSP) are made from H3PO4 and soda ash,
reacted in the proper molecular proportions; the solution is purified if
necessary, evaporated, dried, and milled. TSP is also made from
H3PO4 and soda ash, but caustic soda is necessary to replace the
third hydrogen of the H3PO4. These salts are employed in water
treatment, baking powder (MSP), fireproofing, detergents, cleaners,
and photography (TSP).
When MSPs and DSPs, in correct proportions, or equivalent
mixtures of other phosphates, are heated for a substantial time at
temperatures of between 300 and 500oC and slowly cooled, the
product is practically all in the form of the tripolyphosphate :
NaH2PO4 + 2Na2HPO4 Na5P3O10 + 2H2O

Soda ash and about 75% H3PO4 are reacted in the mix tank. The
orthophosphates are cooled either in a rotary or spray dryer. The sodium
tripolyphosphate is molecularly dehydrated in a gas-fired calciner.
The product is annealed, chilled, and stabilized in a continuous rotary
tempering unit, milled, stored, and packaged.
Certain equipment modifications have been employed, such as addition of
an adjustment mixer, following the reactor mix tank and a spray tower for
drying of the orthophosphate, together with a long, continuous rotary to
carry out the dehydrating (calcining), annealing, stabilizing, and cooling in
one unit.
6. Pyrophosphates
(a) Tetrasodium pyrophosphate (TSPP), Na4P2O7, is used as a
water softener and as a soap and detergent builder. It is
manufactured by reacting H3PO4 and soda ash to yield a DSP
solution, which may be dried to give anhydrous Na2HPO4 or
crystallized to give Na2HPO4.2H2O or Na2HPO4.7H2O. These
compounds are calcined at a high temperature in an oil or gas-
fired rotary kiln to yield TSPP in a plant such as that shown for
TSP.
The relevant reactions may be written as follows:
2Na2HPO4 Na4P2O7 + H2O
2Na2HPO4.2H2O Na4P2O7 + 5H2O
(b) A non-hygroscopic sodium acid pyrophosphate, Na2H2P2O7
(SAPP) is used extensively as a leavening agent in making
doughnuts, cakes, and packaged biscuit doughs. It is
manufactured by partially dehydrating monosodium acid
orthophosphate at temperatures of between 25 and 250 oC over
a period of 6 to 12hr.
The relevant reaction is indicated below:
2NaH2PO4 Na2H2P2O7 + H2O

7. Baking Powders
 The baking powder industry is an important but indirect
consumer of phosphate rock. Baking powder consists of a dry
mixture of sodium bicarbonate (NaHCO3) with one or more chemicals
capable of completely decomposing it, (bicarbonate). The principal
“baking acids” used include: monocalcium phosphate monohydrate,
anhydrous monocalcium phosphate, sodium acid pyrophosphate,
sodium aluminium sulphate, tartaric acid and acid tartrates. A filler
or drying agent, such as starch or flour, is usually added to the active
ingredients to give a better distribution throughout the dough and to
act as a diluent or to prevent the reaction from commencing until
water and heat are applied.
The following equations represent the actions of different
baking powders:

Na2Al2(SO4)4 + 6NaHCO3 6CO2 + 4Na2SO4 + 2Al(OH)3

3CaH4(PO4)2H2O + 8NaHCO3 8CO2 + Ca3(PO4)2 + 4Na2HPO4
+ 11H2O
KH2PO4 + NaHCO3 CO2 + KNaHPO4 + H2O
NaH2PO4 + NaHCO3 CO2 + 2NaHPO4 + H2O
Na2H2P2O7 + 2NaHCO3 2CO2 + 2Na2HPO4 + H2O
KHC4H4O6 + NaHCO3 KNaC4H4O6 +CO2 + H2O

Baking powders must yield not less than 12% available CO 2,

and most powders contain from 26 to 29% NaHCO3 and enough of
 the acid ingredients to decompose the bicarbonate and yield from 14
to 15% CO2. The rest, 20 to 40%, consists of corn starch or flour.

8. Phosphorus Fire-Retardants
Some phosphorus compounds are used as fire-retardants both
in fire-proofing various textiles and for combating forest fires. The
water-resistant fire retardants commonly used for cotton textiles are
a combination of tris-aziridinyl phosphorus oxide (APO) and tetrakis-
hydroxy methyl phosphonium chloride (THPC).
APO is prepared by reacting phosphoryl trichloride and ethylene
imine according to equation (1):

CH2 – CH2 CH2 - CH2

POCl3 + 3 NH base NH PO + 3/2Cl2 (1)
3

THPC is readily made from phosphine and formaldehyde. (eqn. 2):

4CH2O + PH3 + HCl (HOCH2)4 PCl (2)
APO is a very reactive molecule and presumably reacts with
both the hydroxyl groups of cellulose and THPC to form a polymeric
material. For combating forest and bush fires, mixtures based on
(NH4)2 HPO4 or (NH4)2 SO4, thickening agents, colouring matter, and
corrosion inhibitors are most commonly used. It is believed that the
phosphorus compounds act as catalysts to produce non-combustible
gas and char.