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PHOSPHORIC ACID

1. Introduction:
Phosphorus in elemental form and in its many products is derived from commercial deposits of phosphate
rock in the mineral form fluorapatite [ Ca10 ( PO4 )6 F2 ].
Major products of a fully-developed phosphate industry are:
 Phosphorus
 Phosphoric acid
 Ammonium phosphate
 Calcium phosphate Largely as fertilizers
 Nitrophosphate
 Sodium phosphate
 Organic phosphates

2. Consumption Pattern
The phosphorus industry of India is at present tied nearly 100% to fertilizer planning and production.
Consequently, it has grown at the same pace as the nitrogen industries.

Rock Phosphates:
Phosphorus content of rock phosphate is expressed as percentage P2O5 . In trade, it is expressed as bone
phosphate of lime (BPL) which chemically means the tricalcium phosphate content, i.e., Ca3 ( PO4 )2 .
The high grade rock phosphate from Jhamarkotra containing + 30 percent P2O5 is used for
superphosphate manufacture. The rock phosphate from Jhabua and Chattarpur is used for the production of
elemental phosphorus and in fertilizer mixtures. Mussoorie rock phosphate is used for direct application.
About 75 percent of known phosphate occurrences in India are low grade ore with 10 to 25 percent P2O5
and requires prior beneficiation to upgrade P2O5 content to about 30 percent to make it acceptable as feedstock
for fertilizer manufacture.
A commercial beneficiation plant installed by Hindustan zinc, of 600 tpd capacity, to treat the ore from
Maton deposit containing 20-25 percent P2O5 and SiO2 varying up to 30 percent is in operation since 1975. A
200 tpd mobile semi-industrial plant has been installed by RSMML at Udaipur. Based on its experience, a large
commercial beneficiation plant of 2,700 tpd capacity was being installed at Jhamarkotra for beneficiating low
grade (18-20 percent) Jhamarkotra rock containing high dolomite. The commercial plant was expected to be
operative during the end of 1991. For the Jhabua and Lalitpur silicious rock phosphate setting up of a moderate
sized commercial beneficiation plant is under consideration.
Domestic production of rock phosphate during 1990-91 was about5.5 lakh tons. As the demand for rock
phosphate outstrips the domestic supply, bulk of India’s rock phosphate requirements is met through imports
from Jordan, Morocco, Senegal, Florida and Togo. About 3.5 million tons of rock phosphate was imported
during 1990-91.
World phosphate ore reserves are estimated as shown in Table IIF-1
World North South Western Eastern Africa Western Eastern Oceania
America America Europe Europe Asia Asia
67.1 12.9 2.8 1.0 4.0 33.7 2.9 7.1 2.7

World phosphate ore production figures are as shown in Table IIF-2


Table: World Phosphate Ore Production 1982-1984 in 106 t

1982 1983 1984


USA 37.4 42.6 48.4
Mexico 0.4 0.4 0.4
Central and South America 2.8 3.2 3.5
Africa 30.1 33.7 35.5
- Morocco 17.9 20.1 21.2
- Tunisia 4.2 5.9 5.3
Western Asia 9.0 10.2 12.4
- Jordan 4.4 4.7 6.3
Eastern Asia 14.1 14.1 15.0
Western Europe 0.4 0.5 0.5
Australia and Oceania 2.9 2.8 2.8
Eastern Europe 26.6 27.7 28.0

Pertinent Properties:
Yellow phosphorus ( P4 )
Mol. Wt. 123.9
M.P. 44.1 0 C
B.P. 280 0C
Density (gm/cc):
Solid 1.82
Liquid 1.74 (45 0C)
Ignites spontaneously in air, must be stored under water. Possesses disagreeable odor with extreme toxicity.
Red Phosphorus ( P4 )
Mol. Wt. 123.9
M.P. 593 0C
Density of solid 2.36 gm/cc
Exists in at least six different crystal modifications. Formed by heating yellow phosphorus to give a higher
degree of oxidation resistance and stability.
2. Consumption Pattern:
Approximately 18-20% of the phosphate rock processed in the U.S. is initially converted to elementary
phosphorus. The principal derivative of phosphorus in high purity phosphoric acid in a whole range of
concentrations from 50% aqueous grade up to superphosphoric acid (85% P2O5 = 100% H 3 PO4 + 11% free
P2O5 ). These acids go largely to food and detergent industries.
End Uses of Elemental Phosphorus in the USA
Phosphoric acid (high purity and strength
for detergents and food chemicals) 90%
Phosphorus oxychloride (POCI 3 ) 3
Phosphorus trichloride (PCI3 ) 3
Phosphorus pentoxide, red phosphorus for
matches and incendiaries and otherwise 4

3. Methods of Production:
Chemical Reactions
(a ) 2Ca 3 ( PO4 ) 2 + 10C + 6SiO2 � P4 ( yellow grade) + 6CaSiO3 + 10CO
(b) P4 ( yellow grade) � P4 (red grade)
250-450oC

Raw Materials
Low grade, crushed phosphate rock, coke as reductant, and sand as flux
Quantitative Requirements
Basis: 1 ton of yellow phosphorus(93% yield)
 Phosphate rock 7.5 tons at 32% P2O5 to 9.6 tonsat 25% P2O5
 Scan 3.3-3.8 tons
 Coke 1.6-1.8 tons
 Carbon electrode consumption 18-25 kg
 Electricity 12,000-15,000 KWH
 Cooling water 200-250 tons

(b) Plant Capacities: 25-70 tons/day of P per furnace, 2-5 furnaces per plant

Process Description:
Phosphate rock is ground, mixed with a portion of the coke requirement, then sintered into nodules to
obtain better electrical resistivity characteristic and to avoid entrainment of fines in the released P4 and CO
vapors. Screening is necessary to maintain size control with the fines recycled to the sintering operation. Coke
breeze (relatively small particles produced in the coking of coal) and sand are mixed in controlled quantities
based on phosphate rock analysis.

Production of elemental phosphorus, phosphorus pentoxide and phosphoric acid by electric furnace
method.
The electric furnace is 250-300 volt AC-three phase design with power fed to one 100-150 cm diameter
carbon electrode on each phase. The feed charge drops gradually into the fused section of the furnace at 1,400-1,
4500C were the reduction to elemental phosphorus takes place.
The furnace is kept under slight vacuum by fans in the down-stream end of the plant, so the furnace gases
move past an electrostatic precipitator to remove dust and then to a water-cooled condenser. Liquid yellow
phosphorus is collected under water for further processing or shipping. The carbon monoxide (2.5-3 tons/ton P)
is used as fuel or for synthesis gas after clean-up. The mixture is fed to the top shaft of the electric furnace.
The molten slag ( 8 tons/ton of P) from the bottom of the furnace is tapped periodically, cooled and
crushed for road-bed grave, soil liming, and glass manufacture. Where ferrophosphorus by-product is a
substantial part of the slag, either due to high-iron content rock or from scrap iron slugs added intentionally, the
slag must be processed to separate this valuable material. It is sold as an alloy steel additive and for weighting
agents in oil drilling compounds (muds).
Yellow phosphorus is converted to red phosphorus in covered retorts containing a efflux condenser to
retain any evolved P4 vapor. The vessel is gradually heated and the contents melt and slowly change to red
phosphorus. This mass solidifies when approximately 70% has been converted. Since this reaction is
exothermic, heat control must be applied to avoid violent bumping. After a cycle of 6-8 hours, the solidified
mass is cooled, chipped out, washed with aq. Na2CO3 and water to remove residual and unstable yellow P4 ,
then dried and stabilized with 1% MgO.

Wet Process (Strong Sulfuric Acid)


Chemical Reactions
( a ) Ca 3 ( PO4 ) + 3H 2 SO4 + 6 H 2O � 2 H 3 PO4 +3(CaSO4 .2 H 2O )
gypsum

(b) Side reactions


CaF2 + H 2 SO4 + 2 H 2O � 2 HF + CaSO4 .2 H 2O
6HF+SiO 2 � H 2SiF6 +2H 2 O
Raw Materials
The high grade of imported ore is necessary to avoid solubilization of mined rock impurities such as
aluminum, silicon, iron oxides, and alkali minerals. In USA a beneficiation process is used on low-grade ore
which involves milling, screening, hydroseparation, classification.
The only other raw material required is strong sulfuric acid which comes from a contact sulfuric acid
plant located at or near the phosphoric acid plant.
Quantitative Requirements
(a) Basis: 1 ton of 100% H 3 PO4 in 90% yield 2.7 tons of gypsum
Phosphate rock (32% P2O5 ) 2.5 tons
Sulfuric acid (93-98%) 2.0 tons
(b) Plant capacities: 100-150 tons/day of 100% H 3 PO4
Process Description
Phosphate rock is ground to 65% - 200 mesh and fed to a chute where a recycle stream of weak H 3 PO4 washes
it into a reaction tank. Strong H 2 SO4 is metered with automatic control which keeps the acid and rock feed
ration at the desired setting.
A single reactor can be designed by proper baffling and residence time capacitance to permit a 98%
conversion in 4-6 hours. In other designs, a series of 4-5 continuous mixing tanks can be used with slightly
better efficiency of extraction by minimizing back mixing. Heat of reaction is controlled by pulling cooling air
across.
The gypsum-phosphoric acid slurry goes to a traveling pan vacuum filter where the 40% acid is removed
and the cake washed with water. Filtrate from the latter is returned to the reactor. The gypsum is free-filtering
and cake thicknesses of about two inches can be readily obtained. The gypsum can either be dried for use in
plaster, paints and cements, or reacted with ammonium carbonates to give ammonium sulfate (fertilizer
ingredient) and calcium carbonate (Merseberg Process).
The dilute acid is concentrated in a single affect evaporator to any grades > 50% acid. Most of the wet
process acid is being converted to high concentration chemical fertilizers.
Pyrophosphoric acid ( H 4 P2O7 ) can be made by heating the orthophosphoric acid to 250 0C. By
increasing the temperature to red heat ( 900 0C), metaphosphoric acid ( HPO3 ) results.
Major Engineering Problems
(i) Process design
 Fineness of grind-Economic balance between grinding costs and reactor fixed charges as shown by the
curves below:
Figure: Production of phosphoric acid and chemical fertilizer from phosphate rock by strong acid process.

 Temperature-If the temperature is kept above 100 0C, undesirable semi-hydrate ( CaSO4 .1/ 2 H 2O) and
anhydrate (CaSO4 ) crystals are formed which are difficult to filter. By digesting at 80 0C, the gypsum (
CaSO4 .2 H 2O) rhombic crystals predominate and these can be filtered and washed easily.
 Control of sulfuric acid-1-1.5% residual H 2 SO4 is left in the slurry going to the filter, again to produce a
more filterable gypsum. Small percentages of sulfuric acid can be tolerated for fertilizer-grade acid. If a
purer product is desired, the excess H 2 SO4 is eliminated with a slower filtration rate resulting.

(ii) Materials of construction:


 Reaction tanks constructed of steel and lined with acid-proof brick
 All air vent systems are polyvinyl chloride (PVC) coated steel
 Filter is Type 316 stainless steel with polypropylene filter cloth and rubber-lined vacuum receivers of
steel
 Storage tanks of rubber-lined steel

Wet Process (Hydrochloric acid Leaching) (IMI Process)


Chemical Reactions
(a ) Ca 3 ( PO4 ) 2 + 6 HCL + 6 H 2O � 2 H 3 PO4 + 3CaCl2
(b) Side reactions
CaF2 + 2 HCl � 2 HF + CaCI 2
6HF+SiO 2 � H 2 SiF6 + 2 H 2O
Raw Materials
Phosphate rock of high P2O5 content (>30%) is preferred to avoid excessive acid consumption.
Hydrogen chloride gas or concentrated aqueous HCl (>30%)as waste or by-product acid is used. Organic C 4
and/or C5 alcohol solvents are used to extract H 3 PO4 from CaCl2 solution.
Quantitative Requirements
(a) Basis: 1 ton of 100% H 3 PO4 in 98% yield
Phosphate rock (32% P2O5 ) 2.3 tons

Figure: IIF-3 Production of phosphoric acid by HCl leaching.

HCl (100%) 1.4 tons


solvent make-up (Butanol or Amyl Alcohol) 3 kg
Flocculation agent 0.4 kg

(b) Plant capacities: 15-150 tons/day of 100% H 3 PO4


Process Description
Phosphate rock in ground to pass a 20 mesh screen and fed into a dissolver where an acid stream of
conc. HCl plus make-up wash water from the counter-curter-current decantation system is added. Fumes of
CO2 , HF and HCl are scrubbed for acid recovery.
The mixture is feed to a series of decantation units with overflow from the first settler moving to the
curter-current solvent extraction operations. The solids underflow goes to 2-3 washing thickeners.
Extraction of H 3 PO4 plus some free HCl is done in a battery of mixer-settlers (a) with CaCl2 + CaF2
retained in aqueous phase. The extract is again passed through several more mixer-settlers (b) for removal of
trace impurities of Ca++ which are co-extracted. The extractors is aqueous reflux from the next unit-transfer
extractors (c) where water extracts H 3 PO4 and HCL from solvent phase.
The washed solvent is recycled to a final series of mixer-settlers (d) where the balance of HCl is
extracted from raffinate phase of extractors (a). The acid-free brine is sent to steam stripping for solvent
recovery.
The aqueous acid raffinate from © is separated and concentrated in a triple effect evaporator to give
three different overhead streams:
(1) Alcohol-water overhead flash from the first effect which is condensed and returned to extractors (a)
(2) Dilute HCl from the second effect
(3) Conc. HCl from the third effect
The HC1 is returned to acid make-up. The bottoms from the third effect are product phosphoric acid (80%
H 3 PO4 ).
6. Major Engineering Problems
(i) Solvent recovery
The use of relatively expensive solvent in producing low-cost acid means careful attention to design
and operation of solvent-handling equipment.
(ii) Materials of construction
All sections of the plant must be HCl resistant which requires rubber-lined or PVC-lined mild steel or
rigid PVC equipment. The latter is recommended. For evaporation and steam stripping equipment, impervious
graphite (e.g., Karbate, Diabon) is specified.
(iii) Waste disposal
Problems of disposing of CaCl2 aqueous effluent and siliceous rock residue become acute where
lagooning is not allowable.

Electric Furnace Process (Direct Conversion at Plant Site)


Chemical Reactions
(a ) 2Ca 3 ( PO4 ) 2 + 6SiO210C � P4 + 10CO + 6CaSiO3
(b) P4 + 10CO + 10O2 � 2 P2O5 + 10CO2
(c ) 2 P2O + H 2O � 2 H 3 PO4 + ( x - 3) H 2O
Raw Materials
Low grade crushed phosphate rock, coke as reductant, and sand as flux
Quantitative Requirements
(a) Basis: 1 ton of 100% H 3 PO4 in 90% yield; 2.3 tons of by-product slag
Phosphate rock(28% P2O5 ) 2.9 tons
Sand 0.85 ton
Coke breeze 0.5 ton
Air 3,600 Nm3
Electricity 4,800 KWH
Carbon electrode consumption 8 dg
(b) Plant capacities: 60-200 tons/day of 100% H 3 PO4 per furnace, 1-4 furnaces per plant
Process Description
The first part of the electric furnace process is identical with that described under phosphorus until 6the
vapors leave the furnace. The oxidation of these gases is accomplished by an air combustion section down-
stream from the furnace exit. The P2O5 thus formed is removed by spraying the hot gases with water. Some mist
is formed which is next removed by a scrubbing system discussed below.
The crude 85% acid is given (1) an H 2 SO4 treatment to remove entrained calcium salts as CaSO4 , (2)
a powdered silica addition to remove HF, and (3) a counter-current scrubbing with H 2 S to remove arsenic as
AsS3 . The sludge is removed in a sand filter and the acid can be sold as is or diluted to 50 or 75% grades.
Major Engineering Problems
Complete removal of acid mist
A number of methods have been tried to solve this difficult engineering problem. By purely fluid mechanics
designs, a system which includes a Pease Anthony venture scrubber, screens and final water spray has been
successfully adopted. The weak acid recovered from the last two units is used as the knockdown spray fluid for
hydration of P2O5 . A second method, which is probably more successful, uses only a high voltage electrostatic
precipitator after the initial hydrating spray tower.
Materials of construction
High temperature acid brick is used in the furnace and combustion chamber areas. The hydration tower
and other aqueous units are either stainless steel or lead-lined steel. The electrostatic precipitator element is
graphite to resist the action of the free HF steel present.
Electric Furnace Process (Oxidation and Hydration of Elemental Phosphorus)
Chemical Reactions
(a) 2P+2 1 2 O 2 � P2O5
(b) P2O5 + 3H 2O � 2 H 3 PO4
Raw Materials
Elemental phosphorus, air and steam
Quantitative Requirements
Basis: 1 ton of 100% H 3 PO4 in 96% yield
Phosphorus 0.33 ton
Air 1,260 Nm3
Water and steam Not definite
Process Description:
This method of production is used mainly for smaller customer requirement capacities remote from
major phosphoric acid manufacturing facilities.
Phosphorus is melted at 50 0C and metered by water displacement to a steam ejector and atomization
section of the combustion nozzle. Compressed air is injected around the steam atomized phosphorus droplets
and the exothermic reac6tion raises the gas temperature to 2,000 0C. The entire chamber is bout 1.2 m in
diameter and 3.0 m long and is built of stainless steel with water-cooled walls. Both vertical and horizontal units
are used.
The gaseous oxides, partially hydrated, are treated in the same manner as described in the previous
section on conversion of electric furnace gas to 85% H 3 PO4 . Purification is still required to remove arsenic via
H 2 S for making food-grade acid derivatives.
Process Modification to Produce Phosphorus Anhydride:
The burner designed is changed so that no steam is admitted. The air must also be dried by silica gel or
alumina fixed bed adsorption towers. The P2O5 can be condensed as a solid in a large air-cooled tower about 3
m in diameter and 12 m tall. Revolving chains clean off the needles which accumulate on the sides of the vessel.
A new method employs self-agglomeration on small spheroids of P2O5 in a fluidized bed operation. Condenser
size is about 5% of the air-cooled tower unit for the same capacity.
Major Engineering Problems:
In addition to the ones described in Section 5.6, the combustion chamber design and operation for molten
P4 feed required a great deal of development. Under improper operation, a glassy type of metaphosphoric acid
and its polymers can form and drop to the bottom of the chamber, necessitating frequent shut-down and cleanout.
By placing the combustion chamber near the bottom a great deal of the metaphosphoric acid can be vaporized
and passed overhead.
Triple Superphosphate:

Chemical Reaction: [Ca3(PO4)2]3 CaF2 + 14 H3PO4  10 CaH4(PO4)2 + 2HF


Phosphate rock Triplesuperphosphate
Process description:
 A process similar to that for Superphosphate production is used.
 The acid at 60–700C is mixed with ground rock in a conti8nuous mixer and passed to a continuous belt
where reaction is completed in 15–20 minutes.
 The product is granulated, dried and bagged.
 Where a complete fertilizer is desired, excess phosphoric acid is used and neutralized with Ammonia.
Potassium slats are also added.
H2SO4 BY CONTACT PROCESS

Raw materials: SO2 obtained from the following sources: Sulphur (burning), Pickle liquors (FeSO 4 refinery
sludge reuse) Pyrites, Smelter gases(non ferrous sulphide ores)
Process Description: Air - SO2 gas containing 7–10% SO2, 11–14% O2 is preheated by converter gas and sent to
I stage reactors of steel construction. The below reaction occurs at the Sulphur burning stage:
S (s) + O2 (g)  SO2 H = – 70.9 Kcal
The first stage is high temperature (500–600 0C) stage, contains 30% of total catalyst and converts about
80% of SO2.Then the converter product is cooled by heat exchange at 3000C [steam generation] and fed to the
second stage where total yield is increased to 97% by operating at 400–4500C for favourable equilibrium. For
the reaction:

SO2 (g) + ½ O2 (g) SO3 (g) H = – 23.0 Kcal


High yield product gases are cooled to 150 0C by water and air in heat exchangers and absorbed in Oleum
fed at a rate not to allow the acid strength rise beyond 1%. Final scrubbing is done with a lower strength (97%)
acid. Oleum concentrations up to 40% can be made by tower absorption. Higher strength Oleum up to 65% is
prepared by distilling 20% Oleum.
Active catalytic agent: V2O5 (Most widely used) (Earlier Pt catalyst used but gets poisoned easily)
Promoters: Alkali / metallic compounds in trace amounts to enhance activity of catalyst.
Characteristics of Catalyst:
1. Porous carrier to provide large surface area.
2. Pore size controlled &
3. Resistance to process gases at high temperature
Major Engineering Problems:
1. Design of multistage Catalytic converter for exothermic reaction
2. Optimization of space velocity in catalyst chambers
3. Corrosion problems
4. Adoption of process to various types of gas feeds
5. As a result of the problems 1 and 2 above, thin catalyst beds prevail. (30–50 cm height). Yield might drop due
to longitudinal mixing if the convective gas velocity through the bed is too low.
6. Removal of heat of absorption of SO3 in acid. Pumping costs and fixed costs.
Advantages and disadvantages of Vanadium Pentoxide catalyst

Advantages Disadvantages
 Immune to poisons  Must use only dilute SO2 input(7-10%)
 Low initial investment  Larger converters and higher initial investments are
necessary
 Less quantity of catalyst is needed