The Process Technology of

Phosphoric Acid
Gizachew Shiferaw
ChEg 3151
 Processe Technology
• Two different processes can be used in the
manufacture ofphosphoric acid:
1. wet processes, uses phosphate
rock/minerals as raw materials to be digested by
mineral acids H2SO4, H3PO4 ,HNO3 & HCl.

2. The thermal process uses phosphate rock

as basic the raw material with coke, silica and
electrical energy to produce elemental Phosphorus
and then phosphoric acid
• The share of wet phosphoric acid amounts to about
95 % of the total phosphoric acid
• The production of phosphoric acid using the wet
process is preferred over the thermal route because
of the energy costs.
Wet process
Major unit operation in wet process
1.Size reduction: grinding

2. Digestion: Reaction & Crystallization

3.Filteration

4. Evaporation
Wet process general flow diagram

Grinding

Evaporation
Grinding

Evaporation
Wet process general flow diagram

Grinding

Evaporation
Raw materials: phosphate rock & H2SO4
• Most phosphate ores have to be concentrated or
beneficiated before they can be used or sold on
market. Different techniques may be used at the
beneficiation stage, to treat the same ore for
removal of the gangue and associated impurities
• Phosphoric acid technology has to rely on raw
materials of variable consistency and the
technology needs to be constantly adapted to
meet raw materials variations.
• The amounts of impurities introduced into the
process by H2SO4 are generally low or negligible
compared to the amount introduced by the
phosphate rock.
Origin and typical composition of different phosphate rocks
(P2O5 content is highlighted) based on past analysis
1.Grinding
• Depending on the phosphate rock properties
and the process applied, grinding of the
phosphate rock can be necessary. This is
usually carried out using ball or rod mills. Both
types of mills can operate with wet or dry rock.
Some grades of commercial rock do not need
grinding, their particle size distribution already
being acceptable for the dihydrate reaction
section. Most other phosphate rocks require
particle size reduction.
• The energy requirements for grinding depends
on the type of phosphate rock and is about 15
– 18 kWh per tone phosphate rock [9, Austrian UBA,
2002].
 Digestion: Reaction & Crystallization
• The tri-calcium phosphate from the phosphate rock
reacts with concentrated H2SO4 to produce H3PO4 and
the insoluble salt calcium sulphate.

Ca10F2(PO4)6+ 7H2SO4 3Ca (H2PO4)2 +7CaSO4+2HF

Ca3 (PO4) 2 + 3H2SO4 2 H3PO4 + 3 CaSO4

• The insoluble CaSO4 is filtered from the H3PO4.

• Calcium sulphate exists in a number of different crystal
forms depending particularly on the prevailing
conditions of temperature, P2O5 concentration and free
sulphate content.
• Recrystallisation is applied in order to improve the
overall P2O5 yield (P2O5 efficiency).
• The reaction between phosphate rock and H2SO4
is restricted by an insoluble layer of calcium
sulphate which forms on the surface area of the
rock. This restriction is minimised by contacting
the phosphate rock with recirculated H3PO4,
thereby converting as much of it as possible to
the soluble mono calcium phosphate, followed
by precipitation as calcium sulphate with H 2SO4.

Ca3 (PO4) 2 + 4 H3PO4 3Ca (H2PO4)2

3Ca (H2PO4)2 + 3H2SO4 3 CaSO4 + 6H3PO4
 Reaction system operating conditions
• The operating conditions are generally selected so that
the calcium sulphate will be precipitated as the di or
hemihydrate form, i.e. 26 – 32 % P2O5 at 70 – 80 °C for
dihydrate precipitation and 40 – 52 % P2O5 at 90 – 110
°C for hemihydrate precipitation. Circulation of the
reactor contents provides the necessary mixing.
• The reaction system consists of a series of separate
agitated reactors. The multiple vessel reaction system
replaced by a single tank for economy of materials and
space. Some of these single tanks may be divided into
compartments, effectively creating separate reactors.
The slurry temperature is controlled by the use of a flash
cooler. This also de-gases the slurry making pumping
easier. The temperature may also be controlled, for
instance, by using an air circulation cooler.
The filtration stage
• The filtration stage separates the phosphoric acid
from the calci um sulphate. About four to five tonnes
of gypsum are generated for every tonne (P2O5
equivalent) of acid produced.
• The most common types of filtration equipment are
the tilting pan, rotary table or travelling belt.
• The filter medium is moved in sequence through the
various stages for continuous operation.
• The initial separation is followed by at least two-
stages of washing, which ensures that all the soluble
P2O5 is recovered. It is only possible to achieve the
required separation rate if the filtration is either
pressure or vacuum assisted. In practice, vacuum is
invariably used.
At the end of the washing sequence, the remaining
liquid is taken out of the filter cake. The cake is then
discharged and the cloth efficiently washed to avoid
the filter blinding.
The vacuum is released during the discharge of the
cake. It is also beneficial at this point to blow air
through in the reverse direction to assist in the
solids dislodgement. The filtrate and washings are
then separated. They then have to be further treated
under vacuum conditions to de-aerate the product
so that it can be transported under atmospheric
pressure, as a product or for recycling to the
process. The pressure difference is usually
maintained by diplegs into barometric tanks situated
at a level below the separators to be adequate for
hydrostatic head to maintain a balanced vacuum.
 Evaporatoration
• Currently, almost all evaporators are of the forced
circulation design The forced circulation evaporator
consists of a heat exchanger, vapour or flash chamber,
condenser, vacuum pump, acid circulating pump and
associated pipe work. Acid scrubber is usually included
with the system.

• All the evaporators in this service are generally of the

single-effect design because of the corrosive nature of
phosphoric acid and the very high boiling point of the
process. The heat exchangers are fabricated from
graphite or stainless steel with the rest of the equipment
made from rubber-lined steelA multiple effect evaporation
system may be used depending on the
concentration needed.
Forced circulation evaporator for the concentration of H 3PO4

H3PO4

H3PO4
5 Co-product: phosphogypsum

• Gypsum (calcium sulphate/phosphogypsum”) is an

unavoidable co-product in wet phosphoric acid
production
• For every tone of phosphoric acid (P2O5) around 4 – 5
tones of gypsum is produced. Phosphate rock
contains a range of impurities which are distributed
between the product acid and the calcium sulphate.
Because of the volume of the gypsum production and
the type and level of impurities in the gypsum, this co-
product constitutes an environmental challenge.
 6 Co-product:fluosilicic acid
• Most phosphate rocks contain fluoride between 2 – 4 %
w/w. This fluoride is released during acidulation as
hydrogen fluoride, but reacts readily with excess silica
forming fluosilicic acid (H2SiF6). Magnesium and
aluminium compounds also react with HF forming
MgSiF6 and H3AlF6. A proportion of the fluoride is
released in the vapour, the amount depending on the
reaction conditions, with the rest remaining in the acid
solution. Some of this residual amount may combine
with other impurities at a sufficient rate for removal by
filtration. The remaining
amount will appear as sludge in the product acid.
Volatile fluorine compounds can also be present in the
release from the evaporator system.
 2. Types of wet process
• There are three possible subgroups of wet
processes depending on which acid is used for the
acidulation, i.e. HNO3, HCl or H2SO4.
• The wet digestion of phosphate rock with H2SO4 is
the preferred process
1. “Dihydrate process”
2.“Hemihydrate process”
3.“Hemi-dihydrate recrystallisation process,
single-stage filtration”
4.“Hemi-dihydrate recrystallisation process,
double-stage filtration”
5. “Di-hemihydrate recrystallisation process,
double-stage filtration”.
 Thermal process
• The production of thermal phosphoric acid is carried out in two
stages. First, elemental phosphorus is produced from phosphate
rock. Then the elemental phosphorus is oxidized with air to P2O5,
which is subsequently hydrated to produce H3PO4.

• The process starts with the grinding of the phosphate rock.The

ground phosphate rock is mixed with a slurry consisting of water,
silicate/clay, carbon and various waste streams containing
phosphorus, to produce pellets in a granulator.
• The pellets are sintered in a furnace at a temperature of about 800 °C.
Phosphorus is released from the sintered pellets by heating the
pellets to about 1500 °C in an electric resistance furnace together
with cokes (to provide a reducing environment) and gravel (slag
formation). The overall reaction can be summarised as follows:
• The process mainly produces gaseous
phosphorus, carbon monoxide and a liquid
slag. The gas phase is first passed through an
electro filter to remove dust.
• The gaseous phosphorus is recovered
completely through condensation. The
remaining gas phase mainly consists of carbon
monoxide. This gas is used as fuel gas on-site
The left over gas, if any, is flared.
• The liquid slag is tapped from the furnace in batches,
and yields a slag, is used as foundation material in
large construction works, while the latter is used as a
steel additive in the iron and steel industry. The P-
recovery efficiency of the phosphorus process is about
94 %.
• To produce H3PO4, first the elemental P is brought
into a reaction vessel together with air, after which the
phosphorus oxidises to P2O5. The heat evolving from
this reaction is used for the generation of high
pressure steam.
• The P2O5 is contacted with, and reacts with the water
to form H3PO4. Two configurations for this process are
used.
• In one case, the absorption of P2O5 by diluted H3PO4 is carried
out in the same reaction unit as where oxidation of the
phosphorus takes place.
• In the othercase, the reaction of P2O5 to H3PO4 is carried out in a
separate absorption tower, allowing energy recovery as high
pressure steam. The production of H3PO4 from elemental
phosphorus is represented by the following reactions:
Typical consumption levels of inputs
for the production of thermal H3PO4
 Superphosphates
• Superphosphates, i.e. single superphosphate
(SSP) and triple superphosphate (TSP), account
for one quarter of the world’s phosphate
fertiliser production. Superphosphates are
defined by the
percentage of phosphorus as P2O5 and are used
as straight fertilisers (marketable products), but
are also a feedstock for multinutrient fertilisers .
 SSP and TSP manufacturing
• SSP and TSP are manufactured by grinding phosphate
rock very finely and mixed with acid (SSP: 65 – 75 %
H2SO4; TSP: a H3PO4 with a P2O5 content of 50 – 55 %),
giving the following overall reactions:

• In the SSP process, H3PO4 is formed only as an

intermediate. The reactions are rapid (more than96 %
yield) but can continue for several days as the remaining
free acid continues reacting with the excess phosphate
rock. The SSP process retains the calcium sulphate
(CaSO4) in the product
• Ground phosphate rock and acid are mixed in
a reaction vessel. The reaction begins in the
reactor, and is exothermic, reaching
temperatures of 90 – 100 ºC. The slurry is fed
on to a slow moving conveyor belt (the so-
called “den”) or to a holding vessel and held
for a period from 10 to up to 40 minutes.
• The superphosphate is crushed and
afterwards fed to a granulation line(direct
granulation) or to storage (pile) for “curing”
from one to up to six weeks. The
superphosphate can be fed to the granulation
line (indirect granulation) or sold without
further processing from the storage facility.
 Uses of Phosphorus Compounds
• Most Phosphoric acid goes into
fertilizers
• Phosphoric acid often converted to
sodium or ammonium salts

• Na3PO4 used as a cleaning agent

• Used to soften water by ppt Ca, Mg ions
• Polyphosphate salts used as detergent
and in food industry as a buffer and to
improve food storage (TPP)