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Commercial or Industrial manufacturing methods of fertilisers:

[This note is prepared from Text Books, Dryden, Shreve, literature & publication available in the internet
and my personal experience]
Phosphate Fertilizer Terminology
Because of the number of products on the market, the selection of a phosphate fertilizer can be confusing.
An explanation of some terminology may help to avoid some of the confusion. Some important terms are:
Water-Soluble
Fertilizer samples analyzed by a control laboratory are first placed in water and the percentage of the total
phosphate that dissolves is measured. This percentage is referred to as water-soluble phosphate.
Citrate-Soluble
The fertilizer material that is not dissolved in water is then placed in an ammonium citrate solution. The
amount of P dissolved in this solution is measured and expressed as a percentage of the total in the
fertilizer material. Phosphate measured with this analytical procedure is referred to as citrate-soluble.
Available
The sum of the water-soluble and citrate-soluble phosphates is considered to be the percentage that is
available to plants and is the amount guaranteed on the fertilizer label. Usually, the citrate- soluble
component is less than the water-soluble component.
Table 1.: Percentages of water-soluble and available phosphate in several common fertilizer sources
P 2O 5
P 2 O 5 Source

Single Superphosphate (SSP)


Concentrated Triple Superphosphate
(TSP)
Monoammonium Phosphate (MAP)
Diammonium Phosphate (DAP)
Ammonium Polyphosphate (APP)
Rock Phosphate

Total

Available

Water Soluble*

---------------%-------------0
21
20

85

45

45

85

11
18
10
0

49
47
34
34

48
46
34
3-8

82
90
100
0

*Water-soluble data are a percent of the total P 2O5


Source: Ohio Agronomy Guide, Ohio Cooperative Extension Service Bull.472.
Organic Phosphorus Sources:
Organic P fertilizers have been used for centuries as the P source for crops. Even with the advent of P
fertilizer technology processes, organic P sources from animal manuresincluding compostsand
sewage sludge are still very important. From a fertilizer/nutrient management perspective, the major
differentiating factor is the availability of P. As with any of the fertilizer products, especially those with
varying analysis, chemical analysis should be done on these products. Then an availability coefficient
should be used to determine the available P as a portion of the reported total P.

Phosphorus from manure or sludge should be comparable to P from inorganic fertilizer. Therefore, if a
producer has a P recommendation for 30 lbs/A of P 2 O5, applying approximately 65 lbs of 18-46-0 (DAP)
or 6 tons of 11-6-9 (manure, 80% available P coefficient) should provide equivalent results.
The P contained in organic P sources is a combination of inorganic and organic P. Essentially, all of the
inorganic P is in the orthophosphate form, which is the form taken up by growing plants. Diet fed to the
animal has some control on this chemical make-up. Consider P feed supplements and the fact that many
of these could be considered P fertilizers as well. Generally, 45-70% of manure-P is inorganic P. Organic
P constitutes the remaining total P. Much of the organic P is easily decomposable in the soil, but factors
such as temperature, soil moisture, and soil pH all have a bearing on the P mineralization rate. The final
decomposition product is orthophosphate P compounds.
The combination of the organic/inorganic P ratios in the organic P sources and the soil environment affect
the availability coefficient for organic P. Most animal manure research interpretations indicate that
approximately 60-80% of the total P is available to crops in the first year. Due to the chemical
composition of other organic P sources such as bone meal, lesser amounts of plant available P compared
to total P are expected.
Summary:
There are many P-containing fertilizers to satisfy any P recommendation. While organic P sources are
closely associated with livestock operations or with proximity to major metropolitan areas, inorganic
commercial fertilizers are widely available for all. Inorganic P fertilizers have evolved over the last
several decades into a refined, predictable product.

Phosphate fertilisers:
The manufacture of superphosphate involves four steps:
a) Preparation of phosphate rock; (Beneficiation and/or mineral processing)
b) Mixing with acid; (Acidulation with H2SO4, HNO3, HCl, H3PO4 etc) and later Ammonia,
Potassium chloride etc may be reacted or mixed to give a final composition of the fertiliser.
c) Curing and drying of the original slurry; (Slurry as such can be used but expensive)
d) Excavation, milling and bagging of the finished product (, Pellets, Granules, Powders etc).

Note: Beneficiation is a physical process for removal of impurities without any chemical changes of
the mineral or ore but Mineral Processing means enriching ore concentration along with chemical
changes such as decomposition or calcination, incineration, incipient fusion to de-fluorinate etc to a
reasonable extent. Mining of minerals or ores are carried out in different techniques. I) Solid
mining techniques as coal, hematite, magnetite, pyrites, soda ash, lime stone, and different clays etc.
ii) Liquid mining such as that used for petroleum crude lifting from the reservoirs under the
earth.iii) Solution mining such as that used for soluble salts like rock salt in water, Salt-peter / KNO 3
etc. Gas mining such as that used in well known natural gas mining and this perhaps is the one natural
product that is gas-mined so far.

Beneficiation: Mined rock phosphate of the size of lumps or heavy blocks is crushed in a Jaw crusher and
then ground (grinding) to smaller sizes by Hammer or Rod mill. The whole lot mixture of different sizes
of particles are the screened by sieving through into different mesh sizes. These mixtures of various
substances of different densities are then treated in froth \floatation or gravity separation techniques to
both dissolve out the soluble ones and then classified or clarified to get sediments of more concentrated
rock phosphate.
Mineral processing: Calcination or defluorination process:
Raw materials: Rock phosphate, silica, steam or water and fuel.
Main products: Defluorinated phosphate.
By-products: Fluorine compounds.
There are various methods of manufacturing phosphate fertilisers from the beneficiated or( after mineral
processing ) phosphate rock, namely, a) Acidulation, b) Electric-furnace reduction, c) Calcination or
defluorination, d) Calcium metaphosphate process. But the first two are very important commercially and
industrially.
a) Acidulation process:
Raw materials: Phosphate rock, sulfuric acid, phosphoric acid or nitric acid, hydrochloric acid,
In general, acidulation processes for SSP, TSP production, excepting HCl route, all the processes are
practiced commercially.
Main products: Super phosphate, Phosphoric acid (wet process) triple superphosphate, Mono-ammonium
phosphates, Di-ammonium phosphates, Mono potassium phosphate.
By-products: Fluorine compounds, vanadium, uranium etc.
b) Electric-furnace reduction process:
Raw materials: Phosphate rock, siliceous flux, coke (for reduction) electrical energy, Condensing water.
Main products: Phosphorous, and the secondary products wherefrom are Phosphoric acid, triple
superphosphate, various Na, K, NH4, Ca salts, phosphorous pentoxide and halides.
By-products: Fluorine compounds, carbon monoxide, Ferrophosphorous and vanadium.

Industrial Manufacturing methods of normal superphosphate by acidulation


process:
Raw materials: Phosphate rock & sulfuric acid.
The acidulation of phosphate rock with hot concentrated sulfuric acid produces mainly normal
superphosphate as per the following chemical equations
3Ca3(PO4)2]3 .CaF2 +
7 H2SO4
+ 3 H2O = 3 CaH4(PO4)2 . H2O + 2HF + 7 CaSO4
Phosphate rock
(53-57 0 Be)
Mono calcium
Anhydrite
or Fluorapatite
phosphate
Please note that H2SO4 concentration is used in degree Baume ( 0 Be ) and this is the industrial practice.
But for your understanding, convert this into specific gravity and calculate the % of water present. For the
same or different acidulation processes for different products, this H 2SO4 conc. in 0 Be is different and
hence water availabilities are different. More water will facilitate the formation of hemihydrate or
dihydrate of calcium sulphate posing different issues of unit operations as discussed in the class room
discussion.
The above reaction mixture is known as single superphosphate or normal superphosphate.
In the above reaction, an excess of sulphuric acid is consumed by such impurities in the phosphate rock as
CaCO3, Fe2O3, Al2O3, and CaF2. The product increases in weight over the 70 to 75% BPL (bone

phosphate of lime or tricalcium phosphate, where 1% BPL range equals to 0.458% of P 2O5.) phosphate
rock used, as such as 70 % resulting in a superphosphate with 16 -25% P 2O5.
The manufacture of superphosphate involves four steps:
a) Preparation of phosphate rock; (Beneficiation and/or mineral processing)
b) Mixing with acid; (Acidulation with H2SO4 in this case))
c) Curing and drying of the original slurry;
d) Excavation, milling and bagging of the finished product.
Beneficiation:
Most phosphate ores have to be concentrated or beneficiated before they can be used or sold on the
international phosphate market. Different techniques may be used at the beneficiation stage, to treat the
same ore for removal of the gangue and associated impurities. This gives rise to further variations in the
finished ore concentrate product. Phosphoric acid technology, having to rely on raw materials of great
variety, has to readapt itself constantly.
Phosphate rock as mined in the form of pebbles of sizes 1 to 27 mm has a very poor phosphatic value and
is composed of clay slimes ( slime wastes), silica sand and phosphatic pebbles. The pebbles are called
matrix pulverized very finely and received at the beneficiation plant as slurry. There it is washed to
remove clays and fine particles. After the removal of the clay, -16 to 150 mesh feed are sized on inclined
stationery screen. The -16 to 24 mesh fraction is treated in skin flotation operation using Humphrey
spirals to produce spiral concentrate product. Froth flotation circuit of beneficiation is separated into fine
and coarse at 35 mesh for greater overall recovery of the coarser fractions. Flotation reagents such as
saponified fatty acids are added. The coarse concentrates are further treated with another flotation step
using an amine flotation agent. The final concentrate has a 72 to 78 % BPL range. Dried or calcined rock
is ground in roll or ball mills to a fine powder, typically specified as 60 percent by weight passing a 200mesh sieve. Rock is fed into the mill by a rotary valve, and ground rock is swept from the mill by a
circulating air stream. Product size classification is provided by a "revolving whizzer, which is mounted
on top of the ball mill," and by an air classifier. Oversize particles are recycled to the mill, and product
size particles are separated from the carrying air stream by a cyclone.
The pulverized finer rock is used in the process for manufacturing superphosphate with the following
benefits: i) the reaction rate is faster; ii) more efficient use of sulfuric acid; iii) a higher grade of product is
obtained.

Fig: Flow chart for the manufacture of single superphosphate


Process description:

Ground phosphate rock (90% -100 mesh) is fed into a double conical mixer by a weight feeder, where it
is thoroughly mixed with metered quantities of sulfuric acid. The sulfuric acid is diluted with water in the
cone to a concentration of 93%, the heat of reaction serves to heat the sulfuric acid to proper reaction
temperature, and excess heat is dissipated by evaporation of extra water added. The rate of water addition
and acid concentration may be varied to control product moisture. The acid and water are added into the
cone tangentially to provide necessary mixing with phosphate rock. The fresh superphosphate drops into
the den conveyor and allowed I hour time to solidify before reaching the disintegrator. The disintegrator
slices the crude product so that it may be conveyed to the pile storage for curing for 4 to 6 weeks to
complete the chemical reaction and P 2O5 content in the product is increased. The continuous den is
enclosed to arrest the fumes. These fumes are scrubbed with water spray to remove acid and fluoride
before being exhausted to the atmosphere. The scrubbed water is discharged to a lime stone bed to
neutralize the acid.
Acidulation with nitric acid or phosphoric acid or mixed nitric & phosphoric acid is done in the same
process followed by ammoniation. In case of acidulation of phosphate rock with nitric acid, only problem
is that calcium nitrate obtained in the process is very hygroscopic and hence the mixture of calcium
nitrate and superphosphate together is also hygroscopic which is prevented by ammoniation of the mixed
product , followed by drying, and addition of potassium chloride.
Manufacturing of triple superphosphate from phosphate rock:
The triple superphosphate is much more concentrated fertiliser than ordinary superphosphate, containing
more 45 to 46% P2O5 or three times the amount in regular superphosphate. Triple super phosphate is made
by the action of phosphoric acid on phosphate rock; no diluent calcium sulfate is formed.
Raw materials: Phosphate rock & concentrated phosphoric acid
Chemical reaction:
3Ca3(PO4)2]3 .CaF2
+ 14 H 3PO4 10 Ca(H 2PO4)2 + 2HF Fluorapatite
Triple superphosphate
or phosphate rock

Figure: Flowchart of triple superphosphate process


Process description: Pulverized phosphate rock is mixed with phosphoric acid in a two-stage reactor. The
resultant slurry is sprayed into the granulator. The granulator contains recycled fines from the process.
The product from the granulator is dried, screened, the oversize crushed, and cooled again. The final
product is conveyed to the bulk storage, where the material is cured 4 to 6 weeks during which time
further reaction of acid and the rock takes place which increases the P 2O5 content. The exhaust gases from
the granulator and cooler are scrubbed with water to remove silicofluorides.
Non-granular triple superphosphate is manufactured by cone mixer and conveyor belt similar to that used
for normal superphosphate.

Wet-process for manufacturing phosphoric acid:


The processes that use phosphate minerals which are decomposed with an acid, are known as wet
processes and they are the only economic alternative way to Dry process to produce phosphoric acid .
Rapidly increasing demand of fertilisers like triple superphosphate, ammonium and dicalcium phosphates
have led the rapid expansion of manufacturing of wet-process phosphoric acid. Much earlier, most of the
ortho-phosphoric acid was manufactured by the action of dilute sulfuric (50 0 Be) acid on rock phosphate.
This method was supplanted by the Dorr strong acid process, which produced a strong and economical
acid.

However, excepting H2SO4 route to manufacture ortho-phosphoric acid, HNO 3 & HCl routes are not
commercially feasible till now but researches are going on to make it economic and secondly, in the event
of other processes becoming costlier due to prices of existing raw material going higher due, in turn, to
the growing demand of those established processes and raw materials, HNO 3 & HCl routes may find their
applications in the industry in future. However, in this route, although HCl is cheaper than other acids as
above, separation of Phosphoric acid from the reaction mixture from an aqueous solution of phosphoric
acid and calcium salts like CaCl 2 or in case of nitric acid, Ca (NO3) 2 requires additional steps like solvent
extraction with C3-C5 alcohols and /or mixture such solvents and thereafter stripping or distillation as the
case may be for costly solvents recovery. Overall economy will depend on the control of solvent
extraction step. It needs meticulous and innovative research.
Raw materials: Phosphate rock and sulfuric acid (density: ~55 0Be)
Chemical reaction: When raw phosphate rock is digested with sulfuric acid
3Ca3(PO4)2]3 .CaF2
Fluorapatite or phosphate rock

+ 10 H2SO4 + 20 H2O =10 CaSO4.2H2O+ 2HF+ 6H3PO4


~55 0Be

If clear green phosphoric acid is desired, then calcined phosphate rock is digested with sulfuric acid and
the chemical reaction is as follows:
.

Ca3(PO4)2

+ 3H2SO4

Calcined rock

+ 6H2O =

~55 Be

2H3PO4

+ 3 CaSO4. 2H2O
Gypsum

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
Calcium sulphate exists in a number of different crystal forms such as hemi-hydrate, CaSO4, H2O or
dihydrate CaSO4. 2H2O, depending particularly on the prevailing conditions of temperature; P 2O5
concentration and free sulphate content (see Figures below).

Production Processes: Five process routes are discussed in this section and these represent the principal
process routes which are available.

Dihydrate process: The dihydrate process comprises four stages: grinding, reaction, filtration
and concentration and these are represented in figure below.

In the strong acid process, the equipment was lined with lead, stainless steel, hastelloy or acid proof
brick, and sufficient time 1.5 to 12h is provided with vigorous agitation for the reaction to go to
completion. The reaction mixture is cooled using a vacuum (flash) cooler. The reaction temperature in the
digester must be kept low enough and concentration of the acid appropriately maintained to ensure
precipitation of gypsum (CaSO4.2H2O) and not the anhydrite. If the latter is formed, it subsequently
hydrates and causes plugging of pipes. The most common filtration equipment is of three basic types:
tilting pan, rotary table or Travelling belt of which most commonly, the gypsum precipitated is filtered out
using Bird-Prayon tilting pan filter. Acid made from this process is 28 to 32% acids and is used almost
for the fertiliser production, where impurities present are not important. The major end use of this
phosphoric acid is fertiliser 85%.
Another process is the Swenson isothermal phosphoric acid reactor which uses a single vessel vacuum
crystalliser. The advantage of this process is claimed to have reduced capital cost, utilities consumption,
and maintenance cost and high operating efficiency with improved P 2O5 recovery.
Concentration:

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. Currently, almost all evaporators that are being built today for this service are of the
forced circulation design as shown in Figure below
.

This is the most diffused process and the advantages of dihydrate systems are: There is no phosphate rock quality limitation
On-line time is high
Operating temperatures are low
Start-up and shut-down are easy
Wet rock can be used (saving drying costs)
Some grades of commercial rock do not need grinding, their particle size distribution being acceptable
for a dihydrate reaction section (60-70% less then 150m). Most other phosphate rocks need particle size
reduction, generally by ball or rod mills.
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-crystallized with the calcium sulphate
The operating conditions are generally selected so that the calcium sulphate will be precipitated in either
the dihydrate or the hemihydrate form, 26-32% P2O5 at 70-80C for dihydrate precipitation and 40-52%
P2O5 at 90-110C for hemihydrate precipitation.
There are three types of sulphuric acid process, according to the condition of the calcium sulphate
produced, since it can be obtained in the form of anhydrite, hemihydrate or dihydrate. Finally, there
are the processes that obtain a determined final grade in one stage and those that do so in several stages.
Another idea of producing the calcium sulfate hemihydrate (CaSO4. H 2O) instead of usual dehydrate is
advantageous in obtaining 42 to 50% yield of acid directly without involving any cost of evaporation as in
the case of dehydrate but the disadvantage is that the hemihydrate is unstable and could clog the pipes.
The dihydrate process is however still most popular.
Hemihydrate (HH) process
Operating conditions are selected in this process so that the calcium sulphate is precipitated in the
hemihydrate form. It is possible to produce 40-52% P2O5 acid directly, with consequent valuable savings
in energy requirements. Figure below shows a simplified flow diagram of a HH process. The stages are
similar to those of the dihydrate process but grinding may be unnecessary.

The main advantages of this Hemihydrate (HH) process,


Reduction or elimination of evaporation heat requirement cost
Capital savings
Purer acid: Acid from the HH process tends to contain substantially less free sulphate and
suspended solids and lower levels of aluminium and fluorine than evaporated dihydrate process
acid of the same strength.
Lower rock grinding requirements.
A satisfactory rate of reaction can be achieved from much coarser rock than in the dihydrate
process, because of the more severe reaction conditions in the HH process.
The disadvantages of HH systems are:Filtration rate:
Hemihydrate crystals tend to be small and less well formed than dihydrate crystals and thus
hemihydrate slurries tend to be more difficult to filter than dihydrate slurries unless crystal habit
modifiers are used to suppress excessive nucleation.
Phosphate losses:
Scaling: Hemihydrate is not a stable form of calcium sulphate and there is a tendency for it to
revert to gypsum even before the acid has been filtered off.
Filter cake impurity:
Corrosion: The demands on susceptible items of equipment, particularly agitators and slurry
pumps, are increased because of the higher temperature (100 0C) and acid concentration (40-50%
P2O5) compared to a dihydrate plant.
P2O5 Recovery:
Recrystallisation processes:
The best P2O5 recovery efficiencies that generally can be expected in the single-stage dihydrate
and hemihydrate processes considered so far, are 94-96% and 90-94% respectively. The P2O5
losses are retained in the filter cake and this can create problems with disposal or use of the byproduct gypsum. Some of this loss of P2O5 passes into solution and can be recovered when the
calcium sulphate is finally separated, if the calcium sulphate is made to recrystallise to its other
hydrate. This not only raises the overall efficiency of the process but also gives a much cleaner
calcium sulphate.
Several processes have been developed but there are only three basic routes:- Acidulate under
hemihydrate conditions; recrystallise to dihydrate without intermediate hemihydrate separation;
separate product. (Hemihydrate recrystallisation (HRC) process)
Acidulate under hemihydrate conditions; separate product; recrystallise hemihydrate to
dihydrate; filter and return liquors to process. (Hemi-dihydrate (HDH) process)

Acidulate under dihydrate conditions; separate product; recrystallise hemihydrate; filter and
return liquors to process (Dihydrate-Hemihydrate (DH/HH) process)
The phosphoric acid produced by either the wet or the dry process is frequently heated, driving off water
and producing a superphosphoric acid. The phosphate concentration in superphosphoric acid usually
varies from 72 to 76%. The P in this acid is present as both orthophosphate and polyphosphate.
Polyphosphates consist of a series of orthophosphates that have been chemically joined together. Upon
contact with soils, polyphosphates revert back to orthophosphates.
The Haifa process is another wet-process method of producing phosphoric acid by acidulation with
hydrochloric acid in slight excess in combination with an organic solvent ( normally C 3 C4 alcohols) to
extract the phosphoric acid and then water to strip out the phosphoric acid which is concentrated to yield
a high grade phosphoric acid.
With increased cost of sulfur, the sulfuric acid method of acidulation for the production of either
phosphoric acid or superphosphate has been replaced by the nitric acid acidulation method very popularly.
Purification of phosphoric acid so obtained:
Crude wet-process acid is often black and contains dissolved metals and fluorine, dissolved and
suspended organic compounds. Suspended solid materials are usually removed by settling. Solvent
extraction or solvent precipitation method is used to remove the dissolved impurities. Solvent extraction
usually involves a partially miscible solvent, such as n-butanol, iso-butanol or n-heptanol.

Figure: Wet-process phosphoric acid manufacturing flowchart.


The phosphoric acid is extracted and the impurities are left behind. Back-extraction with water recovers
the purified phosphoric acid. Solvent precipitation uses a completely miscible solvent plus alkalis or
ammonia to precipitate the impurities as phosphate salts. After filtration, the solvent is separated by
distillation and recycled.
Uranium is present as a trace amount in the phosphate rock of U.S. , which is recovered because the price
of uranium is pretty high.
ADVANTAGES
Dihydrate Process

Single stage filtration;


Simple design;
Flexibility of rock source;
Proven process;
Ease of operation/shut-down;
Requires lower grades of materials
of Construction;
Wet rock grinding possible;

Low maintenance cost and high


operating factors.
DISADVANTAGES

Produces acid at 26-32% P2O5.


Normally requires steam for
evaporation.
Acid has high levels of F and Al.
P2O5 efficiency 94-96%.
May require rock grinding.
Requires weak acid storage and
evaporation

Easy transport of gypsum slurry.

Hemihydrate Process:
Advantages
Single-stage filtration;
Produces strong acid directly 40-48%
P2O5;
No intermediate storage if acid is
produced
at user's strength;
Uses coarse rock;
Ease of operation;

Disadvantages
Limited number of rocks processed
industrially.
Large filter area required for 48% P2O5
acid.
High lattice loss, low P2O5 efficiency
(90-94%).
Produces impure hemihydrate.
Tight water balance.
Requires higher grade alloys.
Care required in design and shut-down.

A typical fluorine distribution in the dihydrate and hemihydrate processes is:-

Dihydrate
process

Acid

Phosphogypsum

43

Reactor off-gas

Flash cooler vapour


Concentrator vapour

%
15

2
35

Hemihydrate process
%

12

50
8
30

Elemental Phosphorous:
Elemental phosphorous is extracted from rock phosphate by various methods. The element was first
produced on a small commercial scale by treating calcined rock phosphate with sulfuric acid, filtering off
the phosphoric acid, and evaporating it to sp. gr. 1.45. This was mixed with charcoal or coke, again
heated, the water evaporated off, then calcined at white heat in retorts. The phosphorous was thus distilled
off, collected under water, and purified by redistillation.
The production of elemental phosphorous today still depends on volatilization, of the element from its
compounds under reducing condition. Presently, the methods of productions have greatly changed in
details and size of production and elemental phosphorous is manufactured on a large scale as a heavy
chemical.
Raw materials: Phosphate rock, silica and coke.
Reactions: Phosphorous is manufactured by electric-furnace method.
3Ca3(PO4)2 .CaF2 + 9 SiO2 + 15 C CaF2 + 6P + 15CO + 9CaSiO3
or, more simply expressed as,
2Ca3(PO4)2 + 6 SiO2 + 10 C 6CaSiO3 + P4 + 10CO
H = - 3055 kJ
The silica is an essential raw material which serves as an acid and a flux. About 20% of the fluorine
present in the phosphate rock is converted into SiF 4 and volatilized. In presence of water vapour, this
reacts to give SiO2 and H2SiF6.
3SiF4 + 2 H2O 2H2SiF6 + SiO2
The fluorine is not recovered by manufacturer of phosphorous, but the CO is employed as a fuel in
preparing the furnace charge. Ferrophosphorous is tapped as necessary; its quantity is dependent on the
amount of iron originally present as a burden in the rock or added to it.
White phosphorus was first made commercially, for the match industry in the 19th century, by distilling
off phosphorus vapour from precipitated phosphates, mixed with ground coal or charcoal, which was
heated in an iron pot, in retort. The precipitated phosphates were made from ground-up bones that had
been de-greased and treated with strong acids. Carbon monoxide and other flammable gases produced
during the reduction process were burnt off in a flare stack.
This process became obsolete when the submerged-arc furnace for phosphorus production was introduced
to reduce phosphate rock. Calcium phosphate (phosphate rock), mostly mined in Florida and North
Africa, can be heated to 1,2001,500 C with sand, which is mostly SiO2, and coke (impure carbon) to
produce vaporized tetraphosphorus, P4, (melting point 44.2 C), which is subsequently condensed into a
white powder under water to prevent oxidation. Even under water, white phosphorus is slowly converted
to the more stable red phosphorus allotrope (melting point 597 C). Both the white and red allotropes of
phosphorus are insoluble in water.
The electric furnace method allowed production to increase to the point where phosphorus could be used
in weapons of war.
An improved process for manufacturing phosphate nodules from phosphate rock consists of charging the
aggregate phosphate rock into a rotating kiln. The phosphate rock is then heated by a flame that impinges
upon the nodules formed at the exit end of the kiln. The improvement consists of using a higher
temperature flame at the point of impingement of the flame upon the nodules. This is preferably brought
about by adding pure oxygen to the combustionable air mixture.
Calcium phosphate (phosphate rock), mostly mined in Florida and North Africa, can be heated to 12001500 Celsius with sand, which is mostly SiO 2, and coke (impure carbon) to produce vaporized

tetraphosphorus, P4, (mp. 44.2 C) which is subsequently condensed into a white power under water to
prevent oxidation. Even under water, white phosphorus is slowly converted to the more stable red
phosphorus allotrope (mp. 597C). Both the white and red allotropes of phosphorus are insoluble in water.
Gravity delivers the apatite ore, carbon (coke) and silica (gravel) to the submerged-arc furnace through
feed chutes situated in the rood of the furnace ensuring constant packed bed volume. The gaseous
product, consisting mostly out of a mixture of carbon monoxide and phosphorus gas, leaves the furnace
through two symmetrically spaced outlet vents situated above the ferrophosphorus tap hole in the roof of
the furnace. The ferrophosphorus is tapped off, usually once per day. Slag, however, is continuously
tapped through two alternating, water-cooled tap holes located 400 mm above the furnace floor. The feed
material forms the major electrical and flow resistance of the smelting furnace circuit. As the feed
materials descend towards the hot zone in the furnace, they start to soften and melt, significantly lowering
the electrical resistance.

Figure: Phosphorous production flow chart


A conductive path is thus provided between the electrodes where the Joule heating is released to attain the
high temperatures and energy levels necessary to effect the endothermic reactions needed to produce the
phosphorus gas.
Submerged arc furnace: This is so called because the electrodes are immersed deep into the burden
(charge of rock-phosphate plus coke plus silica sand) so as to provide adequate contact for the arc
to interact with the charge and then moderate heating up to softened burden, conductivity of the
charge increases and more current and hence more heating up
to molten burden thereby
facilitating reduction of the rock to gaseous phosphorous and carbon monoxide occurs. It is then
mandatory to lift up the electrode system to allow less power to go into the charge. This way
Electrode system and its material of construction and operation control makes up a huge
engineering activities particularly Electrical, Mechanical & Chemical & metallurgical engineering.
(A). Main application: This type of equipment is mainly used in smelting of metal or non-metallic
materials such as industrial silicon, iron alloy, calcium carbide, matte, yellow phosphorus, boron
phosphate, magnesia and so on.
(B). Equipment Constitution: furnace shell, furnace transformer, high voltage electrical control systems,
low voltage electrical control systems, cooling systems, electrode control device and lifting devices, bus
bar, burn-through device, fume exhaust facilities.
Furnace Construction, Components and Features
Furnace structure and individual components:
A submerge-arc furnace's shell or casing is fabricated from steel. The lower part is lined with hard blocks
of strongly calcined carbon, and the upper part with firebrick. The floor and lower section of the furnace
are water-cooled. Three electrodes are placed at the angles of an equilateral triangle with rounded corners.
These furnaces can be equipped with either pre-baked electrodes or Sderberg electrodes. The Sderberg
electrodes are heated by the electrical current and the furnace heat, then baked solid in the region of the
contact clamps. The electrode must become baked solid over its entire cross section (inside the charge)
when it is fed downwards to compensate for its consumption in the furnace (which is a few centimeters
per hour).

If the electrodes are not completely baked, there is a risk of breakage, especially with long electrodes.
Sderberg electrodes have a higher proportion of organic impurities when compared to the pre-baked
electrodes. Thus, Sderberg electrode-equipped furnaces produce yellow phosphorus and pre-baked
electrodes produce white phosphorus.
Furnace control
Today Electrodes of 2 m in diameter and with current exceeding 150kA are in operation.
The electrode current is kept fairly constant during operation by automatically raising and lowering the
electrodes. When current increases, the electrodes are raised, increasing the electrical resistance between
the electrodes and the furnace floor. Hence reducing the current, produces the opposite effect when the
voltage is kept constant.
Some furnaces are also controlled through either constant voltage or power. From one submerged-arc
furnace, it is possible to produce several ferro alloys. Transformer voltage selection is based on future
changeover of ferro alloys production.
Material flow
Gravity delivers the apatite ore, carbon (coke) and silica (gravel) to the submerged-arc furnace through
feed chutes situated in the roof of the furnace. This ensures a constant packed bed volume. The gaseous
product, a mixture of carbon monoxide and phosphorus gas, leaves the furnace through two
symmetrically placed outlet vents situated above the ferrophosphorus tap hole in the roof of the furnace.
The ferrophosphorus is tapped off, usually once per day. Slag, however, is continuously tapped through
two alternating, water-cooled tap holes located 400 mm above the furnace floor. The feed material forms
the major electrical and flow resistance of the smelting furnace circuit. As the feed materials descend
towards the hot zone in the furnace, they start to soften and melt, significantly lowering the electrical
resistance. A conductive path is thus provided between the electrodes where the Joule heating is released
to attain the high temperatures and energy levels needed to effect the essential endothermic reactions.
Energy consumption
The energy in an industrial phosphorus furnace is distributed between heating up and melting of the
material ( 40%) and chemical reactions ( 45%). Cooling losses (cooling water), electrical losses (Joule
heating) and radiative heat losses account for the rest ( 15%).
Maintenance and safety:
The lifetime of a phosphorus furnace correlates with the durability of its carbon lining. However, new
state of the lining does not require shutting down the furnace and completely emptying it in order to
monitor the status of the lining. Monitoring is instead achieved by incorporating radioactive sources at
points where erosion is known to occur.
Also, special thermocouples are inserted at various depths in the carbon bricks to continuously measure
wall temperature. Wall temperature readings also serve as a maintenance tool, alerting the system to any
irregularities. It is crucial to monitor the position of the wear line in order to avoid hot metal or slag from
breaking through the lining and cause damage to the operators, the furnace and nearby equipment.
In addition, the gaseous product leaving a furnace mostly comprises out of phosphorus tetrahedron (P4)
and carbon monoxide. It still needs to be purified of any dust and is typically sent to an electrostatic gas
purification system.