Copy right material

SINGLE SUPER PHOSPHATE

(SSP) FERTILIZER

Prepared by

Engr. Muhammad Sajid

B.Sc Chemcial Engineering

M.Sc Chemical Engineering

Lecturer

Department of Chemical Engineering, University of Gujrat

1 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid

 Copy right material

HISTORY:

· In 1842 Single Superphosphate was the first industrially produced chemical fertilizer this
is generally attributed to Jhon Bennet Lawes.
· In 1855 the first production were carried in a Barn at the Farm at Rothamsted. The first
factory was located at Deptford Creek near London.
· In 1855 He built a larger plant at Barking, Essex, England
· In 1862 Lawes had mechanized the process to high degree, including continuous mixing
of Sulfuric acid and raw phosphate, and was producing Single Superphosphate at a rate of
100 tons per day.
· The dominance of SSP only really ended in the 1950 - 1960’s when TSP and later DAP
and MAP overlooks it.
· At present the main producing countries are as follows: China, India, Brazil, Egypt,
Australia, New Zealand and Pakistan.

PROPERTIES OF SINGLE SUPER PHOSPHATE:

· ther Name(s): Superphosphate; Enriched

superphosphate; Normal superphosphate;

· molecular formula: Ca(H2PO4)2. H2O

· molecular Weight: 234.05

RAW MATERIALS:

Sulfuric acid and rock phosphate are major raw materials of single super phosphate
manufacturing. Other minor constituents which are required are demineralized water for acid
dilution, fuel (natural gas) for air preheating, air and power.

Detail of major raw materials is as under;

2 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid

 Copy right material

SULFURIC ACID:

Concentrated sulfuric acid (98.5%) is diluted to 60 to 80% with demineral water

depending upon rock phosphate quality and product quality standards. Before feeding in mixer
after dilution dilute acid is cooled below 50 oC.

ROCK PHOSPHATE:

Rock Phosphate is a prime raw material of single super phosphate manufacturing. For production
purposes rock phosphate is ground to powder form. Selection of rock phosphate depends upon its
phosphorous contents which are normally mentioned in the form of P 2O5 contents. The
specifications of rock phosphate vary however average analysis is given below;

TYPICAL COMPOSITION BY WEIGHT

Pakistani Rock Phosphate Morroco Rock Phosphate

P2O5 % 30 - 32 32-35

CaO % 46.24 48-52

SiO2 % 9.87 2.5-5

Al2O3 % 4.87 2max

Fe2O3 % 1.50 1max

MgO % 1.58 0.5max

F % 3.1 3.5-3.6

CO2 % 2.20 4-5

H2O % 0.16 0.8-3

SO3 % 0.35 1.1-1.3

Na2O % 0.31 0.02-0.04

K2O % 0.59 0.02-0.04

Cl2 % 125ppm 0.15%

3 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid

 Copy right material

GRANULAMETRY:

· 98% pass through 100mesh

· 85% pass through 200mesh
· 70% pass through 270mesh (53microns)

FINISHED PRODUCT SPECIFICATIONS:

Different product grades are marketed as per their final phosphorous contents. In Pakistan,
Pakistan standard and quality control authority has mentioned following product standard for
single super phosphate fertilizer.

P2O5 (dry basis) water soluble: 16%

P2O5 (dry basis) available: 18%

Moisture: 5%

Free Acid: 5%

Granulation: 95% between 1 to 5 mm

PROCESS DESCRIPTION

The basic reaction in the manufacture of superphosphate is the reaction of insoluble tri calcium
phosphate, Ca3(PO4)2 which is the major component of rock phosphate with sulfuric acid to
form the soluble mono calcium di-hydrogen, Ca(H2PO4)2.This is described by the following
equation.

1. Ca5(PO4)3F + 5H2SO4→5CaSO4+ 3H3PO4 +HF

2. Ca5(PO4)3F + 7H3PO4 + 5H2O→5Ca(H2PO4).H2O + HF

These reactions can be combined to give the overall equation:

2Ca5(PO4)3F +7H2SO4 + 3H20→7CaSO4+3Ca(H2PO4)2.H2O +2HF

There are other reactions occurring at the same time .For Example Virtually all the HF react with
other silica minerals associated with the fluorapitite (Silicates, quartz) to form silicon tetra

4 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid

 Copy right material

fluoride. These gaseous emissions are recovered as Hydrofluro Silicic acid (H2SiF6) in scrubbing
system. Carbonates in the rock also react with sulfuric acid.

The production of superphosphates consist of following distinct steps

PHOSPHATE ROCK CRUSHING AND GRINDING

Phosphate rock from different sources has different phosphate, fluoride and silica contents. If the
rocks from different sources are used then, these rocks are mixed to produce a product with a
total phosphorus concentration of minimum 13% (29.5% P2O5). The phosphate rock mixture is

Figure 1 Roller Grinder used for Rock Phosphate Lumps Grinding

5 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid

 Copy right material

passed through a Jaw Crusher which reduces the particle size to 2.5cm. The coarsely ground rock
is then passed through an air swept roller mill assembly which reduces the particle size to 70%
passing through 270 mesh screen. The powdered rock is stored in a large hopper. The powder
handling system is fitted with a dust collection system.

MANUFACTURING OF ROP:

Patented process will be used for the manufacturing of ROP in which a catalyst will be used to
enhanced reactivity of rock with sulfuric acid. The ground rock and sulfuric acid are reacted in a
horizontal pre-mixer. A continuous flow of sloppy mix drops out of the pre mixer in to final
mixer and then to Drum Den. The Den has a variable angular speed from 0.5 to 3rpmto adjust the
reaction time depending upon specifications and quality of rock phosphate. Recommended speed
is 0.5 rpm to enable setting of the slurry and release of HF and HSiF6 from the slurry. The
normal reaction time is 30 minutes for the locally available rock.

6 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid

Figure 2 Grinding Unit Process Flow Diagram

 Copy right material

The reaction rate depends upon the rock phosphate and its impurities specially silica contents.
Consequently the final product has 18% available P2O5 and is a mixture of mono calcium
phosphate and calcium phosphate, with predominally about 90% of monocalcium phosphate.
Monocalcium Phosphate is water soluble where as dicalcium phosphate is citrate soluble,
collectively these are known as available P2O5.

The above theoretical reaction for SSP manufacturing is not completely achieved in the Drum
Den because of the secondary reactions occurring in the CaO-P2O5-H20 system. A period of
minimum two weeks is required to attain equilibrium of the reaction; therefore the Green SSP
product is shifted to the storage called Run of Pile (ROP).

A scrubbing system is therefore provided to prevent the pollution of the plant atmosphere by
harmful gases. The hood and hopper assembly are equipped to catch the gases released during
the reaction.

The evolved gases which contain HF and SiF4 are scrubbed in three Stages of washing
equipments, each stage including a cyclonic scrubbing tower in series with venturi scrubber.
Gases from drum den and mixers enter the gas duct where water showers by nozzle. Gas flow
crosses venturi scrubber and scrubbing tower of each stage, water and scrubbing liquors are
recirculated. A combination of Venturi Scrubber with a cyclonic scrubbing tower giving an
excellent contact between the washing liquor and the hazardous gases and absorb efficiently
fluorine and silica.

SCRUBBING OF HYDROGEN FLUORIDE (HF) GAS.

During reaction between rock phosphate and sulfuric acid in mixer and in drum den HF
produced. Recovery and scrubbing of this gaseous product is very important and main problem
on plant as these are highly dangerous and reactive.

HF gas produces as a result of phosphate rock and sulfuric acid reaction in mixer and in den
quickly react with SiO2, present in the system with phosphate rock and produced SiF4 gas.

Reaction is as under

4HF + SiO2 → SiF4 + 2H2O

7 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid

 Copy right material

Hydrogen Fluoride, Tetrafluoro Silicon and water vapors evolved from mixer and den due to
reaction temperature. These gases are sucked from the system using blower and passed through
series of scrubbers. There are three batteries of scrubbers and each battery contains one venturi
and one cyclone scrubber. The whole system of gas scrubbing internally rubber or fiber glass
lined to protect equipments from gases attack. In scrubbers Silicon Tetra fluoride and moisture
reacts to form Gelatinous Silica (Hexafluorosilicic Acid, H2SiF6) as mentioned,

3SiF4 + 2H2O → 2H2SiF6 + SiO2

Figure 3 ROP (SSP) manufacturing Process Flow Diagram

8 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid

 Copy right material

As gases passed through these three scrubber batteries water continuously showered in reverse
flow pattern. Fresh water shower in last scrubber and after testing gas stream discarded through
stack. This scrubbed liquid is partially recycled into the mixer and used as process water and
partially sent to effluent treatment section for treatment and drainage

GRANULATION:

The SSP obtained from ROP section is granulated in granulation section to improve physical &
agriculture properties of fertilizers. The crushers (Jaw Crusher and Hammer Mill) in the ROP
store breaks up any lumps in the product before it is fed to the Granulation drum.
Granulation is performed in a bed of recycled products including fines, crushed oversize, and a
part of proper size product.
For each formula produced, it is necessary to maintain a steady recycle ratio in order achieved
granulation under favorable conditions. The granulation drum rolls and agglomerates the
superphosphate to form granules. Water and steam is sprayed in the granulation drum to facilitate
good granulation. The inclination of the drum and the feed rate determine the retention time and bed
depth. Product discharged from the granulator is then dried in a rotary cylindrical dryer where it is
heated by a co-current stream of hot gases coming from a combustion chamber.

Product from the dryer is classified by screening in order to get three distinct parts; on size
product (the finished product of the required size), fines and oversize. The latter are crushed and
recycled together with fines to the granulator.
Non recycled proper size product is conveyed, as finished product to the final product store and
further sends to the bagging section.
The granulation loop is composed of:
· A granulator
· A dryer
· Double deck screen
· Crushers(Jaw Crusher and two hammer mills)
· Series of belt conveyors and elevator which link the various pieces of equipments
The granulation loop is equipped with a gas scrubbing system enabling
· To get very high efficiency
· To meet the most stringent pollution standards
9 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid
 Copy right material

· To avoid discharging liquid effluents in some cases.

Off-gases from the granulator and the dryer are draught via exhaust fans towards the scrubbing
circuit together with the dusty air collected form conveyors chutes, elevators, screen and
Crusher. Gases from the dryer and from the dedusting circuit are first cyclone and dedusted in
cyclones batteries. The scrubbing is done in 2 steps
· First in venturi type scrubbers (one for dryer gases and other one for granulator gases).
· Second in a cyclonic type scrubber this collects all the effluents of the unit and ensures a
thorough washing (by water) via circulation pumps and cleaning of the effluent gases
before exit to atmosphere.

Figure 4 Process Flow Diagram of granulation section

10 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid

 Copy right material

BAGGING AND STORAGE:

The product to be bagged is reclaimed in storage by pay loader and charged it to conveyer belt
through hopper. The belt conveys material to bagging area where fixed quantity (50 Kg as per
Pakistan standard) of bags are filled & packed. The feeder below hopper contains bucket
arrangement & they are pneumatically controlled or alternatively load cell arrangement. Bagging
unit includes

- Feeding hopper arrangement

- Bagging bin
- Weighing machine
- Sewing machine
- Connecting conveyors/system of belt conveyers.

11 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid

 Copy right material

These final product bags are either stored in neat and clean environment or sent to market
directly. Normally single super phosphate bags are sent to market directly because if humidity of
stored product increases, they agglomerates to hard material which is difficult to handle by
farmers.

Granulated single super phosphate fertilizer is fed to bagging section through screen. On size
material is forwarded and oversize, if agglomerated is mechanically broken down to their
original granules. Normal final product granule size is from 1 to 5 mm in diameter. Undersize, if
present is separated is recycled and treated as dust.

12 SINGLE SUPER PHOSPHATE (SSP) FERTILIZER | © Engr. Muhammad Sajid