PHOSPHORIC ACID

H3PO4

ENGR. MUHAMMAD SAJID

LECTURER
DEPARTMENT OF CHEMICAL ENGINEERING
UNIVERSITY OF GUJRAT,PAKISTAN
Contents
• Properties
• Production
• Wet process
• Blast furnace process

Engr. Muhammad Sajid, UOG

• Electric furnace process
• Oxidation and hydration of phosphorous process
• Uses
• Health safety and environment

2
PROPERITIES
• Formula: H3PO4
• Molar mass: 98 g/mol
• IUPAC ID: trihydroxidooxidophosphorus
phosphoric acid

Engr. Muhammad Sajid, UOG

• Density: 1.89 g/cm³
• Boiling point: 158 °C
• Melting point: 42.35 °C
• Solubility: Water
• Appearance: White solid or colourless, viscous
liquid (>42C)
• Odor: Odorless 3
PRODUCTION OF PHOSPHORIC ACID
• Phosphoric acid (H3PO4) can be produced by
these commercial methods:

Engr. Muhammad Sajid, UOG

1) Wet process or from sulfuric acid and
phosphate rock
2) Using phosphate rock and blast furnace
3) Using phosphate rock and electric furnace
4) Oxidation and hydration of phosphorous
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PHOSPHORIC ACID
• The concentration of phosphoric acid is normally
expressed as % P2O5 (percent phosphoric anhydride)
rather than % H3PO4 (percent phosphoric acid).

Engr. Muhammad Sajid, UOG

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WET PROCESS
• RAW MATERIALS
 Basis: 1000kg phosphoric acid (100%)
 Phosphate rock = 1635kg
 Sulfuric acid = 1360kg

Engr. Muhammad Sajid, UOG

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 WET PROCESS

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WET PROCESS
• Wet process is by far the most common route
and the acid can be used in phosphate fertilizers
production (DAP, MAP, SPA).
• In a wet process facility, phosphoric acid is

Engr. Muhammad Sajid, UOG

produced by reacting sulfuric acid (H2SO4) with
naturally occurring phosphate rock.
• The reaction also forms calcium sulfate (CaSO4),
commonly referred to as gypsum.
• The insoluble gypsum is separated from the
reaction solution by filtration. 8
WET PROCESS
• The basic chemistry of the wet process is exceedingly simple.
The tricalcium phosphate in the phosphate rock is converted
by reaction with concentrated sulphuric acid into phosphoric
acid and the insoluble salt calcium sulphate.
Ca3(PO4)2 + 3H2SO4 + 6H2O 2H3PO4 + 3CaSO4.2H2O

Engr. Muhammad Sajid, UOG

• 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.
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WET PROCESS
• 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

Engr. Muhammad Sajid, UOG

sulphuric acid.
Ca3(PO4)2 + 4H3PO4 3Ca(H2PO4)2
Ca(H2PO4)2 + 3H2SO4 3CaSO4 + 6H3PO4
• Calcium sulphate exists in a number of different crystal
forms depending particularly on the prevailing conditions
of temperature, P 2 O 5 concentration and free sulphate
content 10
WET PROCESS
• The operating conditions are generally selected
so that the calcium sulfate will be precipitated in
either the dihydrate or the hemihydrate form.
• Thus producing 26-32% P2O5 at 70-80°C for

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dihydrate precipitation and 40-52% P2O5 at 90-
110°C for hemihydrate precipitation.
• Further evaporation of the solvent can be
performed for a high-concentration phosphoric
acid.
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Grinding of rock materials
Wet or dry grinding of Phosphate rocks is required
depending upon the raw materials. Fine grinding is required
in case of multi-compartment digesters and poor sulfate
control. Most of the old plants use dry grinding, and a

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majority of the new plants use wet grinding with a ball mill
or ring roller mills having air classification. Slurry containing
62 to 70% solid is produced. Wet grinding requires about 30
to 40% less power and there is no atmospheric pollution by
dust. The main disadvantages of this process are that the
balls and the mill lining wear out faster, and the amount of
recycled waste water that may be required in phosphoric
acid production is reduced. Also, it is necessary to maintain 12
the ratio of solids while grinding.
Handling and Storage of Phosphate Rock

Phosphate rock are stored in dry conditions and

protected against rain, wind and freezing weather.
Relatively coarse rocks can be stored in piles. To

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ensure the constant supply, the storage capacity
should ideally be 1.5 times the largest shipment.

13
 Amount of Sulfuric Acid
• As the by-product acid may contain some impurities, most
phosphoric acid plants have on site facilities for producing
sulfuric acid from sulfur or pyrites. Sulfuric acid of 93 to 98%
concentration is used.
• The sulfuric acid requirement is calculated assuming its

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amount required to combine with calcium present in the rock
to form calcium sulfate.
• Also, considering that about 15% of fluorine combines with
calcium oxide to form calcium fluoride, the sulfuric acid
requirement is calculated.
• For a high grade phosphate rock, H2SO4 required is 2.5 tons
per ton of phosphorus; and for low grade rocks, it is 3.15 tons 14
per ton of phosphorus.
 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

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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, 15
phosphoric acid concentration, etc.
CONT…..
• The filtration rate is also affected by temperature,
concentration, viscosity of the acid, the desired recovery, the
amount of vacuum, the design of the filter and insoluble
impurities in the rock like clay. The normal filtration rates

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reported in the production are 2 to 18 tons/m2/day.

16
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 sludge usually contains gypsum, fluosilicates, iron and
phosphate compounds. Acids containing sludge can be used

Engr. Muhammad Sajid, UOG

for onsite fertilizer (triple superphosphate) production.
• Most of the phosphorus (as P2O5 ) in the sludge is citrate-
soluble but not water soluble.
• The sludge may be used in the production of non- granular
mono-ammonium phosphate which is used as an
intermediate in the production of compound fertilizers.
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Purification
• There is no economical method for using sludge solids
where phosphate fertilizers are sold on the basis of water
solubility.
• Precipitation after concentration to 54 % phosphorus (as
P2O5 ) is slow and never so complete as more precipitate
will form on standing.

Engr. Muhammad Sajid, UOG

• Elemental phosphorus is produced by an electric furnace. At
a high temperature, a mixture of phosphate ore, silica and
carbonaceous material (coke, coal etc.) produces calcium
silicate, phosphorus gas and carbon monoxide.
• The P and CO off-gases from this reaction are cooled under
water to isolate solid phosphorus. Alternatively, the P and
CO off-gases can be burned with air to produce phosphorus
pentoxide and carbon dioxide. 18
 PURIFICATION
19

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Using phosphate rock and electric furnace
• Thermal process phosphoric acid is of a much higher purity
process.
• This process is used in the manufacture of high grade
chemicals, pharmaceuticals, detergents, food products, and
other non fertilizer products.
• Very pure phosphoric acid is obtained by burning

Engr. Muhammad Sajid, UOG

elemental phosphorus to produce phosphorus pentoxide,
which is subsequently dissolved in dilute phosphoric acid.
• This route produces a very pure phosphoric acid, since most
impurities present in the rock have been removed when
extracting phosphorus from the rock in a furnace. The end
result is food-grade, thermal phosphoric acid; however, for
critical applications, additional processing to remove arsenic 20
compounds may be needed.
Electric Furnace Process

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REACTIONS
Ca3(PO4)2 + 3SiO2 + 5C 2P + 5CO + 3CaSiO3 ∆H=-364.8 Kcal

2P + 5CO + 5O2 P2O5 + 5CO2

Engr. Muhammad Sajid, UOG

P2O5 + 3H2O 2H3PO4 ∆H=-44.9 KCal yield

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Using phosphate rock and
blast furnace
• The blast furnace process was widely used in the first three
decades of 20th century. Resulting phosphoric acid can be
used in manufacturing of insecticide, pesticides, detergents
etc. but not for fertilizers.

Engr. Muhammad Sajid, UOG

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 Blast Furnace Process
24

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Blast Furnace Process
Reactions
Ca3(PO4)2 + 3SiO2 + 5C 2P + 5CO + 3CaSiO3

2P + 5CO + 5O2 P2O5 + 5CO2

Engr. Muhammad Sajid, UOG

P2O5 + 3H2O 2H3PO4 85-90% yield

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 OXIDATION AND HYDRATION OF
PHOSPHOROUS
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.

Engr. Muhammad Sajid, UOG

Combustion of phosphorous increases the temperature
up to 1980C. 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.

2P + 2½O 2P2O5 26
P2O5+ 3H2O 2H3PO4 (94 – 97% yield)
27

Engr. Muhammad Sajid, UOG

OXIDATION AND HYDRATION
OF PHOSPHOROUS
• 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 H3PO4 of
75% to 85% concentration. Remaining acid is trapped into

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packed column or electrostatic precipitator.

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LABORATORY ROUTES
• A demonstrative process consists in the oxidation of red
phosphorus by nitric acid.

1/ Pn + 5 HNO3 → H2O + H3PO4 + 5 NO2

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n

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USES
• Used for preparation of hydrogen halides
• Used as a "rust converter", by direct application to rusted
iron, steel tools, or surfaces. It converts reddish-brown
iron(III) oxide, Fe2O3 (rust) to black ferric phosphate, FePO4

Engr. Muhammad Sajid, UOG

• Food-grade phosphoric acid is used to acidify foods and
beverages such as various colas.
• Used in dentistry and orthodontics as an etching solution, to
clean and roughen the surfaces of teeth where dental
appliances or fillings will be placed.
• As an ingredient in over-the-counter anti-nausea medications
that also contain high levels of sugar (glucose and fructose). 30
USES
• Used in many teeth whiteners to eliminate plaque.
• Used as an external standard for NMR and HPLC
• As a chemical oxidizing agent for activated carbon
production

Engr. Muhammad Sajid, UOG

• As the electrolyte in phosphoric acid fuel cells and is used
with distilled water (2–3 drops per gallon) as an electrolyte
in oxyhydrogen (HHO) generators.
• Also, used as an electrolyte in copper electro polishing for
burr removal and
• circuit board planarization.
• As a flux by hobbyists (such as model railroaders) as an aid to 31

soldering.
USES
• As common wet etching agent in compound semiconductor
processing,
• Hot phosphoric acid is used in micro fabrication to etch silicon
nitride (Si3N4 ). It is highly selective in etching Si3N4 instead
of SiO2 , silicon dioxide.
• As a cleaner by construction trades to remove mineral

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deposits, cementitious smears, and hard water stains.
• As a chelant in some household cleaners aimed at similar
cleaning tasks.
• Used in hydroponics pH solutions to lower the pH of nutrient
solutions.
• As a pH adjuster in cosmetics and skin-care products.
• As a dispersing agent in detergents and leather treatment.
• As an additive to stabilize acidic aqueous solutions within 32
specified pH range
HEALTH SAFETY
AND
ENVIRONMENT

Engr. Muhammad Sajid, UOG

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HEALTH & SAFETY
• Phosphoric acid is a corrosive liquid of low toxicity that may
cause burns on skin and eye contact and irritation in the
respiratory tract.
• Prolonged contact may be necessary before some

Engr. Muhammad Sajid, UOG

individuals notice burning or irritation of the skin.
• Sustained skin contact with phosphoric acid may cause
dermatitis at the site of contact.
• Ingestion may cause burns in the digestive zone.
• Inhalation of spray may cause irritation in the respiratory
tract and can cause lung oedema.
• Contact with strong caustic substances must be avoided as 34
the reaction is exothermic and produces splashes.
HEALTH & SAFETY
• Phosphoric acid is not explosive or flammable but in contact
with ferrous metals less resistant than type 316 stainless
steel, it liberates hydrogen gas which is explosive in the
range 4-75% by volume of hydrogen in air.
• A dangerously high concentration of fluoride gases often
builds up in phosphoric acid storage tanks.

Engr. Muhammad Sajid, UOG

• Workers handling phosphoric acid should be well informed
by supervision of the hazards involved and should be
instructed in safety procedures.
• Suitable protective clothing, goggles and masks should be
worn as required.
• Workers should be shown the location of first aid and safety
35
equipment, such as showers, eye baths, or other emergency
sources of water and instructed in their use.
GYPSUM DISPOSAL
• Around 5 tonnes of gypsum are generated per tonne of P2O5
produced as phosphoric acid.
• This represents a serious disposal problem with the individual
phosphoric acid production units.
• Two methods can be used to dispose of gypsum:-
 – Disposal to land

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 – Disposal into water
• By-product gypsum contains four types of impurity that are
considered to be potentially harmful:-
 – Residual acidity (P 2 O 5 )
 – Fluorine compounds
 – (These are only harmful if disposal is into fresh water because disposal
into sea
 water results in the formation of insoluble calcium fluoride.) 36
 – Undesirable trace elements
 – Radioactivity
GYPSUM DISPOSAL
To WATER
• The gypsum can be pumped through an outfall into the sea
at coastal sites and estuaries.
• Disposal into rivers is no longer practised, as it is not a good
environmental option.

Engr. Muhammad Sajid, UOG

• Disposal of gypsum into the sea has the advantage that
gypsum is more soluble in sea water than in fresh water.
However, some of the impurities in the gypsum should be
controlled. Clean gypsum itself (CaSO 4 ) is soluble and is not
harmful to the environment.
• A phosphoric acid plant with high efficiency is essential for
this method of disposal and only lean phosphates an e 37
used in the plant if the pollution is to be kept within local
environmental quality standards.
GYPSUM DISPOSAL
To LAND
• Under proper conditions land disposal is the best
environmental option although it is not possible
everywhere because it requires space and certain
soil qualities where the gypsum stack is situated.

Engr. Muhammad Sajid, UOG

• Dry gypsum from the filter in some plants is
transported by belt conveyors to the gypsum
storage pile.
• The pile area is completely surrounded by a ditch
which collects the run-off water including any rain
water 38
Emissions into air
• Emissions from the stack ( For new Plants):-

Fluoride 5mg.Nm-3 (40 g.t-1 P2O5)

Dust/particulates 50mg.Nm-3

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• Emissions from the stack (For existing plants):-

 Fluoride 30mg.Nm-3 (40 g.t-1 P2O5)

 Dust/particulates 150mg.Nm-3

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Emissions into air
• Emissions from gypsum piles and pond areas:-
• No detectable effect on the environment is
normally found from fluoride emissions in cases of
worldwide wet and dry gypsum stacking and no

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standard measurement techniques or limits exist.

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Emissions into water
• New plants must ensure total recycle of both the
process water and the water used for the transport
and disposal of phosphogypsum.
• Most existing plants with open-loop systems in
reactors and evaporators can be converted to

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closed-loop type so process water disposal is
eliminated. Should this not be entirely possible, the
highest limitation in disposal is to be sought and the
effluent treated.
• Similarly water used for the transport and disposal
of phosphogypsum shall be kept in a closed loop to
the greatest possible extent compatible with the
permitted gypsum disposal. 41
Solid wastes
• In new plants the phosphogypsum should be disposed of
to land. The system should be designed to prevent any
contaminated water from reaching the surrounding ground
water system.
• For existing plants where water disposal has been

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practised in the past, such disposal in the future will be
limited to 10-20% of the gypsum provided that the
disposal of the gypsum is demonstrated as being
acceptable to the receiving water.
• The choice between storing the gypsum on land or
disposal into the sea (if re-use is not possible) depends on
the local situation and the impurity levels in the gypsum. 42
• When disposal into the sea is the only available option, a
plant with a proven, high phosphate efficiency (above
97%) and an appropriate rock phosphate should be used
to keep the contamination within acceptable limits.

Engr. Muhammad Sajid, UOG

• Environmental monitoring shall be carried out
systematically to ensure that no harm is caused to the
receiving medium and the effluent treated if necessary.

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QUIZ 1: HISTORY & ACID INDUSTRY

Any

Engr. Muhammad Sajid, UOG

Question?
Thanks 44