Chapter 4: Phosphorus Industries

Phosphorous & Phosphoric acid

Phosphate rock
Phosphoric acid

Physical Properties of Phosphoric Acid

Chemical formula H3PO4

Molar mass 97.99 g·mol−1

Appearance Colorless, viscous liquid (>42 °C)

Odor Odorless

1.885 g/mL (liquid)

Density 1.685 g/mL (85% solution)
2.030 g/mL (crystal at 25 °C)

Boiling point 158 °C

Solubility in water 392.2 g/100 g (at −16.3 °C)

Phosphoric acid (Uses)
 The major use is for production of fertilizers (85%)
 Used as a "rust converter”.
 Food-grade phosphoric acid is used to acidify foods and beverages. It is
used as a flavoring agent in carbonated beverages Coca-Cola, beer, jams,
jellies and cheeses.
 Used in many teeth whiteners (toothpaste) to eliminate plaque.
 As a chemical oxidizing agent for activated carbon production.
 As a pH adjuster in cosmetics and skin-care products.
 As a dispersing agent in detergents. In the manufacture of detergents,
phosphoric acid is used to produce water softeners (tripolyphosphate). Water
softeners remove Ca2+ and Mg2+ ions from hard water.
 Phosphoric acid is used as the electrolyte in many fuel cells.
 In the steel industry, it is used to clean and rust-proof the product.
Phosphoric acid - Raw Materials
 Phosphate rock (PR) is a globally accepted but imprecise term
describing any naturally occurring geological material that contains
one or more phosphate minerals suitable for commercial use.
Phosphoric acid Production
Two different processes can be used in the production of phosphoric acid:
1) The Thermal Process:
 Phosphate rocks as the basic raw material with coke, silica and
energy are used to produce elemental phosphorus and then phosphoric
acid.
 This process has been abandoned because of the amount of energy which
is needed.
2) The Wet Process:
 Uses phosphate rocks as raw materials, to be digested by mineral acids
such as; H2SO4, HNO3 and HCl.

 The share of wet phosphoric acid amounts to about 95 % of the total

phosphoric acid production.

 The production of phosphoric acid using the wet process is preferred

over the thermal route because of the energy costs and it is the only
economic alternative way to produce phosphoric acid.
Phosphoric acid Production- Thermal Process
Raw materials for the production of phosphoric acid by the thermal process are
elemental (yellow) phosphorus, air, and water. Auxiliary components are
coke & silica.
The production of phosphoric acid by thermal process is carried out in three
stages.
Stage 1: Production of elemental phosphorus from phosphate rock.
Stage 2: Oxidation of elemental phosphorus with air to produce P2O5,
Stage 3: Hydration of P2O5 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 (reacted) in a furnace at a temperature of about
800°C.
Phosphoric acid Production- Thermal Process
 Phosphorus released from the sintered pellets is by heating the
pellets to about 1500°C in a furnace together with cokes (to
provide a reducing environment) and gravel (slag
formation).
 The overall reaction can be summarized as follows:

 The furnace can be either :

 Blast furnace

 Electric resistance furnace

Phosphoric acid Production- Thermal Process

 From the furnace, gaseous phosphorus, carbon monoxide

and liquid slag are produced. 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 %.
Phosphoric acid Production- Thermal Process
 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 other case, 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
Phosphoric acid Production- Thermal Process

H3PO4
Phosphoric acid Production- Thermal Process
Blast furnace
 Resulting phosphoric acid from blast furnace can
be used in the manufacturing of insecticide,
pesticides, detergents etc. but not for
fertilizers.
 Phosphate rock is pulverized and mixed with
coke powder and binder and 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 .
 Preheated air leads to burning of briquettes giving
temperature rise up to 15000C.
 The coke act as reducing agent as well as fuels.
Phosphoric acid Production- Thermal Process
 Outlets for removal of slag and ferro-phosphorous are provided at
the bottom of the furnace.
 Reaction is completed in the furnace itself producing P2O5 and calcium
silicates as slag.
 The product gases also contain carbon monoxide and nitrogen along
with dust particles.
 For purification, it is passed through cyclone separator and
phosphorous condenser. Thus, P2O5 and elemental phosphorous are
separated out.
 Hot P2O5 gases are cooled in the heat exchanger.
 the entire phosphorous and phosphorous pentoxide is cooled and purified
before taken into hydrating towers. Purification of phosphoric acid includes
removal of arsenic followed by filtration.
Phosphoric acid Production- Thermal Process
Phosphoric acid Production- Thermal Process
Electric Resistance Furnace
 The phosphate rock is reduced to elemental phosphorous by the
action of coke and heat in the presence of sand in electric arc furnace.
 Subsequent oxidation of phosphorous gives phosphorous
pentoxide which on hydration gives the product phosphoric acid.
 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 1095ºC is maintained in electric furnace so that maximum
amount of elemental phosphorous extracted out and oxidation takes
place.
 Fluoride of phosphorous and calcium are the common impurity which
reacts with sand giving fluorosilicates as the slag.
 Concentrating the product acid and filtering it as final product.
 Note:- The advantage of this process lies in its ability to use a
low-grade phosphate rock.
Phosphoric acid Production- Thermal Process
Phosphoric acid Production- Wet Process
 Wet process also called production of phosphoric acid from sulfuric
acid and phosphate rock.

 In the wet process acids (such as sulfuric acid, nitric acid or

hydrochloric acid ) are 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 basic chemistry of the wet process is exceedingly simple. The

tricalcium phosphate in the phosphate rock is converted by
reaction with concentrated sulfuric acid into phosphoric acid and
the insoluble salt calcium sulphate.
Phosphoric acid Production- Wet Process
 There are two processes i.e. dehydrate and (CaSO4.2H2O) and
hemihydrates (CaSO4.½H2O) are used for production of phosphoric
acid.
 The operating conditions are generally selected so that the calcium
sulphate will be precipitated in either the dehydrate or the hemihydrates
form.
 Dehydrate and (CaSO4.2H2O) = 26-32% P2O5 and operation
temperature 70-80°C.
 Hemihydrates (CaSO4.½H2O) = 40-52% P2O5 at operating
temperature of 90-110°C.
 The reaction between phosphate rock and sulfuric acid is self-limiting
because an insoluble layer of calcium sulphate forms on the surface
of the particles of the rock.
Phosphoric acid Production- Wet Process
 In order to get a maximum conversion, the rock will be in contact with
recirculated phosphoric acid.
 Grinding/ size reduction of the raw material is important to increase
the surface reaction. (this is related with the surface area/volume ratio).

 Wet process phosphoric acid normally contains 26 to 30% P2O5.

 In most cases, the acid must be further concentrated to meet phosphate
feed material specifications for fertilizer production.
 Depending on the types of fertilizer to be produced, phosphoric acid is
usually concentrated to 40 to 55% P2O5 by using 2 or 3 vacuum
evaporators.
Phosphoric acid Production- Wet Process

 Major unit operation in the wet process

 Size Reduction: grinding
 Digestion: Reaction and Crystallization
 Filtration
 Evaporation.
Phosphoric acid Production- Wet Process

The Wet Process General block Diagram

Phosphoric acid Production- Wet Process

Size Reduction: 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 dehydrate 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 – 18kWh per tone phosphate
rock.
Phosphoric acid Production- Wet Process

Digestion: Reaction and Crystallization

The tri-calcium phosphate from the phosphate rock reacts with
concentrated H2SO4 to produce H3PO4 and the insoluble salt calcium
sulphate.

The operating conditions for dihydrate precipitation are 26-32% P2O5 and
70-80°C.
The insoluble CaSO4 is filtered from the product (H3PO4).
Calcium sulphate exists in a number of different crystal forms particularly
depending on the prevailing conditions of temperature.
Phosphoric acid Production- Wet Process

Digestion: Reaction and Crystallization

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 minimized by contacting the phosphate rock with
re-circulated H3PO4, thereby converting as much of it as possible to
the soluble mono calcium phosphate, followed by precipitation as
calcium sulphate with H2SO4.

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

3Ca(H2PO4)2 + 3H2SO4 3CaSO4 + 6H3PO4
Phosphoric acid Production- Wet Process
Filtration
 The filtration stage separates the phosphoric acid from the
calcium sulphate. About four to five tonnes of gypsum are
generated for every tonne (P2O5 equivalent) of acid produced.
 It is only possible to achieve the desired degree of separation at a
reasonable rate if the filtration is either Vacuum/Pressure assisted
and in practice vacuum is always used. : The most common types of
filtration equipment are then Rotary Drum Filter.
 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.
Phosphoric acid Production- Wet Process
 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.
Phosphoric acid Production- Wet Process
Concentration/ Evaporation
 Currently, almost all evaporators are the forced circulation design.

 The forced circulation evaporator consists of a heat exchanger, vapor

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 steel.

 A multiple effect evaporation system may be used depending on the

concentration needed.
Phosphoric acid Production- Wet Process
Concentration
Phosphoric acid Production- Wet Process