Inorganic Industries Engineering

‫هندسة الصناعات غريالعضويه‬

Lecture 4
Dr.: Sameh Araby El-Mekawy
Outlines

Manufacture of Phosphoric acid

Phosphoric acid
Phosphoric acid (PA) is an important industrial chemical used as
an intermediate in the fertilizer industry, for metal surface
treatment in the metallurgical industry (for protection against
corrosion). and as an additive in the food industry. In medicine,
PA combined with zinc powder forms zinc phosphate, which is
used as a dental cement.

Properties
 Chemical formula H3PO4
 Mineral acid
 P2O5 is the anhydride of phosphoric acid.
 Also known as orthophosphoric acid or phosphoric(V) acid
 White solid or colorless, viscous liquid (>42 °C)
Methods of H3PO4 production
Phosphoric acid is made by two processes:
a) the 'wet' process
b) thermal process
The thermal method normally produces a more concentrated
and purer product, but is energy intensive (because of the
manufacture of phosphorus itself. Acid produced by the 'wet'
route is less pure but is used in the manufacture of fertilizers.
'wet' process is characterized by relatively high production
volume, low cost and low purity.
1. Thermal process
• Thermal process phosphoric acid is commonly used in the
manufacture of high grade chemicals, pharmaceuticals,
detergents, food products which require a much higher
purity.
• This process has been abandoned because of the amount of
energy which is needed.

Raw Materials
Elemental (yellow) phosphorus, air, and water.
Process Description
 The raw materials for this process are phosphorus and air:
Oxidation stage

 Initially, phosphorus is sprayed into the furnace and is burnt in air at

about 1800-3000 K.
 Most processes use undried air and many involve the addition of
steam to the phosphorus burner to produce and maintain a film of
condensed polyphosphoric acids which protect the stainless steel
burner tower (externally water cooled). The products from the burner
tower pass directly into a hydration tower where the gaseous
phosphorus oxide is absorbed in recycled phosphoric acid:
Hydration stage

 Alternatively, the phosphorus may be burnt in dried air. The

phosphorus pentoxide is condensed as a white powder and separately
hydrated to phosphoric acid.
• Burning and direct hydration, as previously described,
creates highly corrosive conditions. The equipment is
constructed from stainless steel or is carbon brick-lined. To
reduce corrosion, the walls of the burner and hydrator
towers are cooled.
• Concentration of phosphoric acid (H3PO4) produced from
the thermal process normally ranges from 75 to 85 percent.
This concentration is required for high grade chemical
production and other non-fertilizer product manufacturing.
 Thermal Process Emissions and Controls
• The major source of emissions from the thermal process is
phosphoric acid mist (H3PO4) contained in the gas stream
from the hydrator. The particle size of the acid mist ranges
from l.4 to 2.6 micrometers (μm). It is not uncommon for
most of the total phosphorus pentoxide (P2O5) to be present
as liquid phosphoric acid particles suspended in the gas
stream. Efficient plants are economically motivated to
control this potential loss with various control equipment.
• Control equipment commonly used in thermal process
phosphoric acid plants includes venturi scrubbers
(REPORT), cyclonic separators with wire mesh mist
eliminators, fiber mist eliminators, high energy wire mesh
contractors, and electrostatic precipitators (ESP).
Venturi scrubbers
2. Wet processes
• The majority of phosphoric acid, approximately 96 percent, is
produced using the wet process method.
• In these processes, phosphoric acid can be obtained by digesting
phosphate rock in mineral acids such as nitric, hydrochloric,
phosphoric, or sulfuric.
• The process using sulfuric acid is the most common among all
particularly for producing fertilizer grade phosphoric acid.
 Raw Materials
1- Phosphate rocks:
 Fluorapatite Ca10(PO4)6(F,OH)2
 Francolite Ca10(PO4)6–x(CO3)x(F,OH)2+x
 Both rocks contain many impurities: fluoride (F-), chloride (Cl-),
iron, aluminum oxides (Fe2O3 and Al2O3), pyrites (ferrous sulfide,
FeS), and fossilized organic matter. These all interfere with
production procedures, impair the PA quality, and enhance
corrosion and deterioration of metallic and plastic materials used
for fabrication of equipment and rubber linings for reactor walls.
 The high grade of imported ore is necessary to avoid solubilization
of mined rock impurities such as aluminium, silicon, iron oxide,
and alkali minerals.
2- Sulfuric acid
The only other raw material required is strong sulphuric acid which
comes from a contact sulphuric acid plant located at or near the
phosphoric acid plant.
General description of wet Process
 The phosphate rock is dried, crushed, and then continuously fed
into the reactor along with sulfuric acid.
 Phosphoric acid is produced by reacting sulfuric acid (H2SO4) with
naturally occurring phosphate rock in a series of well-stirred
reactors. .
 The reaction combines calcium from the phosphate rock with
sulfate, forming insoluble calcium sulfate (CaSO4), commonly
referred to as gypsum.

 The insoluble calcium sulphate is then separated from the

phosphoric acid, most usually by filtration.
 The reaction between phosphate rock and sulphuric acid is self-
limiting because an insoluble layer of calcium sulphate forms on the
surface of the particles of the rock. This problem is kept to a minimum
by initially keeping the rock in contact with recirculated phosphoric
acid to convert it as far as possible to the soluble monocalcium
phosphate and then precipitating calcium sulphate with sulphuric acid.
Ca3(PO4)2 + 4H3PO4→ 3Ca(H2PO4)2
Ca(H2PO4)2 + 3H2SO4 → 3CaSO4 + 6H3PO4
 There are many impurities in phosphate rock, the amounts and
proportions of which are very variable.
 There are side reactions during digestion; for example with calcium
fluoride and calcium carbonate present in the rock:

 The "fluoride part" of the apatite is either removed as gaseous silicon

tetrafluoride in the presence of silica and absorbed in scrubbers as
aqueous hexafluorosilicic acid, or is largely removed as the sparingly
soluble sodium hexafluorosilicate by adding a sodium compound. Part
of the fluoride remains in the acid.
 Fluorosilicilic acid is an important by-product from this operation. It
is also used to make aluminum fluoride, used in turn in the
manufacture of aluminum.
 The crystal structure of the calcium sulfate formed depends on the
conditions of the reaction. At 340-350 K, the principal product is
dihydrate, CaSO4.2H2O. At 360-380 K, the hemihydrate is produced,
CaSO4.1/2H2O.
 Calcium sulfate is filtered off and the acid is then concentrated to ca
56% P2O5 using vacuum distillation.
 The product from the 'wet process' acid is impure but can be used,
without further purification, for fertilizer manufacture. Alternatively it
can be evaporated further to ca 70% P2O5, a solution called
superphosphoric acid which is used directly as a liquid fertrilizer.
Types of Wet process
 There are three types of wet process,
according to the condition of the
calcium sulphate produced, since it can
be obtained in the form of
1) anhydrite CaSO4,
2) hemihydrate CaSO4.1/2H2O or
3) dihydrate CaSO4.2H2O.
 The hydrate form is controlled mainly
by temperature and acid concentration.
26-32% P2O5 at 70-80°C for
dihydrate precipitation and 40-52%
P2O5 at 90-110°C for hemihydrate
precipitation.
Types of Wet process
 Anhydrite (n=0) process is not commercially viable due to high
temperatures requirement and the higher rate of corrosion.
 The dihydrate process is the most popular due to simplicity and ability
to use a wide variety of phosphate rocks in the process.
 Hemihydrate process has the advantage of producing wet process
phosphoric acid with a higher P2O5 concentration and less impurities
than the dihydrate process.
Dihydrate process
Most wet process phosphoric acid is still produced by the dihydrate
process.
Advantages of dihydrate systems are:-
 There is no phosphate rock quality limitation
 Simple design.
 Operating temperatures are low
 Start-up and shut-down are easy
 Wet rock can be used (saving drying costs)
The disadvantages are:-
 Relatively weak product acid (26-32% P2O5)
 High energy consumption in the acid concentration stage
 4-6% P2O5 losses, most of them co- crystallised with the calcium
sulphate
Process Description
The dihydrate process comprises four stages: grinding, reaction,
filtration and concentration.
(1) Grinding
Some grades of commercial rock do not need grinding, their particle
size distribution being acceptable for a dihydrate reaction section (60-
70% less then 150μm). Most the phosphate rocks need particle size
reduction, generally by ball or rod mills. Both mills can operate with
wet or dry rock.
Size Reduction
 Size reduction refers to all the ways in which particles are cut or broken into
smaller pieces.
 The objective is to produce small particles from big ones for any of the
following reasons:
1. To reduce chunks of raw materials to workable sizes e.g. crushing of mineral
ore.
2. To increase the reactivity of materials by increasing the surface area.
3. To release valuable substances so that they can be separated from unwanted
material.
4. To reduce the bulk of fibrous materials for easier handling.
5. To meet standard specifications on size and shape.
6. To increase particles in number for the purpose of selling.
7. To improve blending efficiency of formulations, composites e.g. insecticides,
dyes, paints
Principles of size reduction
Most size reduction machines are based on mechanical compression or
impact. When a solid is held between two planes and pressure is applied on
one plane, the solid is fractured and breaks into fragments when pressure is
removed. The fragments formed are of different sizes. An example of an
industrial equipment that is based on compression is a jaw crusher. Impact is
the breaking up of material when it is hit by an object moving at high speed.
The product contain coarse and fine particles. A ball mill is based on impact.
 Jaw Crusher
Composition
A jaw crusher consists of a vertical fixed
jaw and another swinging jaw that
moves in the horizontal plane. In the
corresponding diagram, the jaws are
coloured red. The two jaws make 20-30o
angle between them. The swinging jaw
closes about 250 to 400 times/min. Feed
is admitted between the jaws. It is
crushed several times between the jaws
before it is discharged at the bottom
opening.

 A jaw crusher produces a coarse

product.
Ball Mill
 Ball Mill
 A ball mill is a tumbling mill generally used for previously crushed materials.
 It is generally used to grind material 6mm and finer, down to a particle size of 20 to 75
microns.
 The mill consists of a cylinder containing a mixture of large and small steel grinding balls
and the feed. When the cylinder is rotated, the rotation causes the balls to fall back into the
cylinder and onto the material to be ground. The rotation is usually between 4 to 20
revolutions per minute, depending on the diameter of the mill. The larger the diameter, the
slower the rotation. If the speed of the mill is too great, it begins to act like a centrifuge
and the balls do not fall back, but stay on the perimeter of the mill. The point where the
mill becomes a centrifuge is called the critical speed. Ball mills usually operate at 65% to
75% of the critical speed.
 A ball mill is suitable for dry- or wet- milling of various material in cement, fertilizer,
metallurgical industries and other industries.
(2) Reaction
 The tricalcium phosphate is converted by reaction with
concentrated sulphuric acid into phosphoric acid and insoluble
calcium sulphate. The reactor maintains an agitated reaction
volume in circulation.
 The reaction system consists of a series of separate agitated reactors
 The operating conditions: 26-32% P2O5 and 70-80°C.
 This temperature is controlled by passing the slurry through a flash
cooler, which also de-gasses the slurry and makes it easier to pump.
 The temperature can also be controlled by using an air circulating
cooler.
(3) Filtration
 This stage separates the phosphoric acid from the calcium
sulphate dihydrate.
 5 ton of gypsum are generated for every 1 ton (P2O5) of product
acid produced.
 The filter medium must move in sequence through the various
stages for continuous operation. The initial separation must be
followed by at least two stages of washing, to ensure a satisfactory
recovery of soluble P2O5. It is only possible to achieve the desired
degree of separation at a reasonable rate if the filtration is either
pressure or vacuum assisted and in practice vacuum is always
used. All modern plants use continuous horizontal vacuum filters
(REPORT).

 The gypsum can either be dried for use in plaster, paints, and
cements, or reacted with ammonium carbonates to give
ammonium sulphate and calcium carbonate.
(4) Concentration
There is a long history of direct contact concentrators, in which
evaporation is effected by bringing the acid into intimate contact with
hot combustion gas from a burner, enabling equipment walls to be
made of materials and in thicknesses which are suitable for efficient
indirect heat transfer.
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.
 Phosphoric acid is manufactured in Egypt by treating the local phosphate
ores with mainly sulfuric acid (wet process). The produced acid is
accompanied by the solublization of major part of the heavy elements and
uranium contained in the ores. Some of these elements which have been
considered of special concern are; Cu(II), Cd(II) , Zn(II) and Pb(II) that
have been distinguished as hazardous substances. Beside the presence of
uranium which cause a radiological environmental contamination. The
presence of these impurities affects the quantity and the quality of the
product. For this reason, about 95% of the acid produced by the wet-process
is directly used as fertilizers and excluded from the use in non-fertilizer
applications
Wet Process Emissions and Controls
 Gaseous fluorides such as silicon tetrafluoride (SiF4) and hydrogen fluoride
(HF) are major emissions from wet process acid production.
 Phosphate rock contains 3.5 to 4.0 percent fluorine. Part of the fluorine from
the rock is precipitated with the gypsum, another part is leached out with the
phosphoric acid product, and the remaining portion is vaporized in the
reactor or evaporator. The relative quantities of fluorides in the filter acid and
gypsum depend on the type of rock and the operating conditions. Final
disposition of the volatilized fluoride depends on the design and operation of
the plant.
 Scrubbers may be used to control fluoride emissions. A number of different
scrubbing systems have been used for removing fluoride. These can vary
both in the scrubbing liquor and in the type of scrubber used. The most
widely used scrubber is the void spray tower operating at atmospheric
pressure but others, such as packed bed, cross-flow venturi and cyclonic
column scrubbers have been extensively employed.
Major Eng. Problems in wet-process phosphoric
acid WPA production
 Selection of phosphate rock
As phosphate rock is a complex raw material that affects plant operation in
numerous ways. The quality of the product is strongly influenced by the impurities
in the phosphate rock.
 Process design:
WPA plants operate under severe conditions that include elevated
temperatures and rapid heat transfer, high acid concentration,
agitation and circulation of liquids containing erosive suspended
solids, aeration, formation of foam, and volatilization of corrosive
acidic vapor that condenses on cooler metallic surfaces. Destructive
corrosion results from combinations of these factors in which their
combined action is greater than the sum of their separate actions.
 Material of construction:
 The prime consideration during the selection of construction materials for the
plant structures and equipment is their corrosion resistance. The central
problem of WPA appears in the huge reactor, fitted with Stainless-steel
agitators, pumps, and ducts. The corrosion intensity depends on the P2O5/F
ratio of the PR feed to the reactor.
Reaction tank constructed of steel and lined with acid-proof brick.
All air vent systems are PVC coated steel.
Storage tanks of rubber-lined steel.
 Two additional problems are the emission of fluoride pollutant volatile
gases, mist, and fumes through the reactor chimneys and the form and
size of the gypsum crystals, which affect filterability in the filtration
stage, plugging the filters with scales and sludge. In the concentration
stage, particularly when producing food-grade acid (85%–95%
H3PO4), heavy metals (Cu, Cd, Cr, Pb, Hg, and V) contaminate and
impart an undesirable tint. Great efforts are invested to partially remove
or eliminate these contaminates by analytical, chemical, and
electrochemical procedures.
 Economics of the production will be highly influenced by the proximity of
the phosphate mine to the plant (i.e. transportation cost), presence of a
sulfuric acid plant nearby (for availability of low-cost steam and H2SO4),
location of the plant in an already industrialized area (to have the
infrastructure and possible availability of water for wet grinding) and the
end use of the phosphoric acid which determines the load on concentration
units.