H3PO4
H3PO4
H3PO4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Module: 4
Lecture: 21
PHOSPHORIC ACID
INTRODUCTION
MANUFACTURE
The modern manufacturing methods of phosphoric acid are following:
The blast furnace process was widely used in the first three decades of 20 th
century. Resulting phosphoric acid can be used in manufacturing of insecticide,
pesticides, detergents etc. but not for fertilizers.
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Raw materials
Basis: 1000kg phosphoric acid (100%)
Phosphate rock = 2290kg
Sand (Silica) = 6800kg
Coke = 3175kg
Briquette binder = 227kg
Air = 450000ft3
Reactions
Ca3(PO4)2 + 3SiO2 + 5C 2P + 5CO + 3CaSiO3
2P + 5CO + 5O2 P2O5 + 5CO2
P2O5 + 3H2O 2H3PO4 85-90% yield
Manufacture
Steam
To phosphorous plant
precipitator
collector vapour boiler
Cottrell
Binder Coke
Sand
Briquetic
Phosphate Water
press
Hydrater
rock pressure
5000 psi Compressed
Air
air
Hot
Blast
blast
Furnace
stove
Phosphoric
acid
Slag
Ferro
phosphorous
Animation
Phosphate rock is pulverized and mixed with coke powder and binder is
compressed to 5000 psi resulting into the briquettes. Briquettes are dried and
charged along with sand and additional coke powder from top of the blast furnace.
The preheated air (1000 – 11000C)is charged from bottom of the blast furnace via
tuyere. A tuyere is cooled copper conical pipe numbering 12 in small furnace and
up to 42 in large furnace through which hot air is blown in to the furnace. Preheated
air leads to burning of briquettes giving temperature rise up to 13700C. The coke acts
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Engineering aspects
Blast furnace
Blast furnace is made of high temperature resistant refractories brick. Blast
furnace have accessories of hot blast stove for supply of compressed preheated air
having temperature 1000 – 11000C, briquette press for preparation of briquettes of
Phosphate rock and coke, dust collector (cyclone separator) for removal of dust
particles from product stream. Also, two outlets for removal of slag and
ferrophosphorous are provided at the bottom of the furnace.
The top of the blast furnace is closed as it operates at high top pressure. There
are two different systems are used for charging of briquettes, coke and silica. One is
having double bell system which is often equipped with movable throat armour and
other is bell less top as shown in figure.
Also, there are two construction techniques to support the blast furnace as
shown in figure.
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Animation
One utilized lintel or support ring at the bottom of the shaft upon which the
higher level of the furnace rests. The other is free standing construction requiring
and independent support for the blast furnace top and gas system. The required
expansion both thermal as well as pressure for the installation is below for the lintel
i.e. in bosh/belly area in lintel type furnace, while compensator for expansion in the
free standing furnace is at the top.
Raw materials
Basis: 1000kg phosphoric acid (100%)
Phosphate rock = 2225kg
Sand (silica) = 680kg
Coke breeze = 400kg
Caron electrode = 8kg
Air = 100000ft3
Electricity = 4070KWH
Reactions
Ca3(PO4)2 + 3SiO2 + 5C 2P + 5CO + 3CaSiO3 ΔH = - 364.8 kcals
2P + 5CO + 5O2 P2O5 + 5CO2
P2O5 + 3H2O 2H3PO4 87-92% yield ΔH = - 44.9 kcals
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Manufacture
Water CO2
Sand
Coke Sand
breeze filter
precipitator
Water
Cottrell
Sintering
Phosphate
&
Hydrater
rock
Sizing
Water
Size Electric
Ferro Furnace Purifier
phosphorous 2400 oF H2S / H2O
Phosphoric acid 85 %
Air
Figure: Manufacturing of Phosphoric acid using Electric furnace
Animation
Phosphate rock after proper grinding and primary purification is taken into
sintering oven where it is nodulized and granulized so that fast oxidation of the
separated phosphorous takes place. Temperature of 10950C is maintained in electric
furnace so that maximum amount of elemental phosphorous extracted out and
oxidation takes place. Since fluoride of phosphorous and calcium are the common
impurity which reacts with sand giving flourosilicates as the slag.
The gases from the furnace, phosphorous and carbon monoxide are
removed by the suction process and the oxidation product P2O5 is taken into
hydration column which gives P2O5 to H3PO4 at about 850C. Purification of
phosphoric acid is carried out by H2S to remove Arsenic, H2SO4 to remove calcium
salts and Silica to remove fluorides. All the byproducts are removed before
concentrating the acid and filtering it as final product.
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Raw materials
Reactions
2P + 2½O2 P2O5
P2O5 + 3H2O 2H3PO4 (94 – 97% yield)
Manufacture
At the locations away from phosphate rocks mines from purified elemental
phosphorous is oxidized and hydrated to give phosphoric acid. In the manufacturing
process molten phosphorous is sprayed into combustion chamber along with
preheated air and superheated steam. Combustion of phosphorous increases the
temperature up to 19800C. Furnace design depends on the requirement with
respect to quantity and quality. They are made of acid proof structural bricks,
graphite, carbon and stainless steel.
Animation
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Water
COMBUSTION
CHAMBER
Hydrater
Phosphorous
seperator
Cyclone
Glass wool
Air
filter
Steam
Seperator
Vent
Cooler
The gases from furnace which mainly contains P2O5, steam, N2 and small
quantity of oxygen is taken into a hydration column where counter current mixing of
dilute phosphoric acid and the gases gives the product concentrated H 3PO4 of 75%
to 85% concentration. Remaining acid is trapped into packed column or
electrostatic precipitator.
The wet process is according to the acids (sulfuric acid, nitric acid or
hydrochloric acid) used to decompose the phosphate rock. The process using
sulfuric acid is the most common among all particularly for producing fertilizer grade
phosphoric acid.
The wet process phosphoric acid, also called as green acid. Depending upon
the hydrate forms of calcium sulfate produced during the wet process, it is classified
as anhydrate, hemi hydrate and dihydrate. The hydrate form is controlled mainly by
temperature and acid concentration.
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
The dihydrate process is the most popular due to simplicity and ability to use
a wide variety of phosphate rocks in the process. Hemihydrate processes produce
phosphoric acid of a relatively high concentration without the need of the
concentration step. There is also some attentiveness in the two-stage processes that
involve crystallization in the hemi-hydrate form followed by recrystallization in the
dihydrate form, with or without filtration or centrifugation.
Raw materials
Basis: 1000kg phosphoric acid (100%)
Phosphate rock = 1635kg
Sulfuric acid = 1360kg
Reaction
Ca10F2(PO4)6 + 10H2SO4 + 20H2O 10CaSO4.2H2O + 2HF + 6H3PO4
Manufacture
There are two processes i.e. dihydrate and hemihydrates (CaSO4.2H2O and
CaSO4.1/2H2O) are used for production of phosphoric acid.
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Hot
Air Water
Suction Water
Vaccum
Gypsum
To Product acid
Waste
Figure: Manufacturing of Phosphoric acid by Wet process
Animation
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Three methods of cooling are generally in use: (a) blowing air on to the slurry,
(b) blowing air across the slurry, and (c) flash cooling under vacuum.
The fumes emerging from the reactors and the digesters are sent to the
fluorine recovery unit, while the suspension of the digesters are filleted in the first
compartment of a continuous filter, which yields phosphoric acid containing about
33% of P2O5.
Engineering aspects
Selection of phosphate rock
The plant is designed in such a way that can be used for blend of rocks from
different sources. The plants have extra capacity for grinding, filtration and slurry
handling systems to take care of variation in the rock composition. As phosphate
rock is a complex raw material that affects plant operation in numerous ways, a
thorough chemical and mineralogical evaluation of the quality should be made
before selecting a phosphate rock or changing the source to another. However, a
trial run in a pilot plant is needed for complete evaluation of the rock. The
phosphate rock used in the process is of as high a grade as possible, usually ranging
from 30 to 35 % P2O5 and 1 to 4 % iron and aluminum.
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Filtration of gypsum
Filtration is carried out as efficiently and economically as possible. All modern
plants use continuous horizontal vacuum filters. The other widely used filters are tilting
pans, rotary filters, rotary table filters and belt filters. Some of the product acid is
recycled to the digestion step to control the percentage of solids in the slurry, which
is normally 35 to 45 %.
Filters are characterized by their surface area and the rate of rotation (in a
rotary filter) or the rate of travel (in a belt filter). The filtration rate is also affected by
the size and shape of gypsum crystals which, in turn, are decided by the type of
phosphate rock, crystal shape modifiers, control of reaction conditions, sulfate
concentration, slurry re-circulation, phosphoric acid concentration, etc.
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
Purification
Phosphoric acid which is intended for use in fertilizers does not require any
purification but for chemical and food products it must be purified. The block
diagram of purification processes is as follows.
H3PO4
NaOH or Na2CO3 (Impure)
Adjustment to pH
Na2SiF6
=2
H2S BaCO3
Adjustment to pH
As2S3, BaSO4, PbS, etc.
=5
Fe
Reductions
Ca(OH)2
Adjustment to pH
Al(OH)3, Fe(OH)3, Mn(OH)2,
= 8.5
H2SO4 MnO(OH) etc.
Precipitation of
anhydrous and hydrated
CaSO4
H3PO4
Purified
Sludge disposal
The sludge usually contains gypsum, fluosilicates, iron and phosphate
compounds. Acids containing sludge can be used for onsite fertilizer (triple
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
PROPERTIES
Molecular formula : H3PO4
Molecular weight : 97.994gm/mole
Appearance : White solid or colourless viscous liquid above 420C
Boiling point : 1580C (decompose)
Melting point : 42.350C (anhydrous)
29.320C (hemihydrate)
Density : 1.885gm/mL (liquid)
1.685gm/mL (85% solution)
2.030gm/mL (crystal at 250C)
Solubility : Soluble in water
Viscosity : 147cP (100%)
USES
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Module: 4
Dr. N. K. Patel
Lecture: 21 Phosphoric acid
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