THERMAL PROCESS

1. Electric Furnace Process a. Direct conversion at plant site b. Oxidation and Hydration of Elemental Phosphorous 2. Blast Furnace Process

Phosphate Rock Fines Recycle Air

Co ELECTRIC FURNACE METHOD for Fuel or Synthesis gas

H2O

Sintener

ElectroStatic Precipitator

Water Spray Condenser

Coke Breeze

Sand
250-300v 3 Phase AC Power

Fines To Waste`

H2O

Yellow Phosphorous storage

CO

1400 C Slag Electric furnaces Air cooled

P2O5 Route

Combustion Chamber
CO

H2O

Electrostatic Demister

P4,CO,Dust

Ambient Air(Not Dried)

H2SO4

Purified 85% H3PO4

Combustion chamber

Powdered SiO2

Fluid Bed Condenser

Crushed Slag

Bone dry air via silica gel

Phosphoric Anhydride P2O5

H2S

Sludg

Purification Process

PHOSPHOROUS
INTRODUCTION:

Phosphorous in elemental form and its many products is derived from commercial deposits of phosphate rock in the mineral form Fluorapatite [Ca10(PO4)6F2].

PHYSICAL PROPERTIES

YELLOW PHOSPHOROUS

RED PHOSPHOROUS

Mol wt. = 123.9 Melting Point = 44.1C Boiling Point = 280C Density (gm\cc): Solid = 1.82 Liquid = 1.74

Mol wt. = 123.9 Melting Point = 593C Density (gm\cc): Solid = 2.36

RAW MATERIALS

Phosphate Rock Conc. H2SO4 Water

CHEMICAL REACTIONS

2 Ca3(PO4)2 + 6 SiO2 + 10 C -> P4 + 10 CO + 6 CaSiO3 P4 + 10 CO + 10 O2 -> 2 P2O5 + 10 CO2 P2O5 + 2 CH2O -> 2 H3PO4 + (x-3) H2O

Phosphate Rock Fines Recycle Air

PRODUCTION OF P,P2O5
ElectroStatic Precipitator

Co for Fuel or Synthesis gas

H2O

Sintener

Water Spray Condenser

Coke Breeze

Sand
250-300v 3 Phase AC Power

Fines To Waste`

H2O

Yellow Phosphorous storage

` 1400 C Slag Electric furnaces Air cooled

P4,CO,Dust
P2O5 Route

CO
Combustion chamber
Fluid Bed Condenser

Crushed Slag

Bone dry air via silica gel

Phosphoric Anhydride P2O5

VARIOUS STEPS INVOLVED

Grounding Screening Electric Furnace Chemical Reactions Molten slag

GROUNDING

Phosphate rock is ground, mixed with a portion of the coke requirement, then sintered into nodules to obtain better electrical resistivity characteristics and to avoid fines in the released P4 and CO papers.

SCREENING

Screening is necessary to maintain size control with the fines recycled to the sintering operation. Coke breeze and sand are mixed in controlled quantities based on phoshpate rock analysis.

ELECTRIC FURNACE

The electric furnace is 250-300V AC three phase design with power fed to one 100-150 cm diameter carbon electrode on each phase. The feed charge drops gradually in to the fused section of the furnace at 1400-1450C where the reduction to elemental phosphorous takes place.

CHEMICAL REACTIONS

The furnace is kept under slight vacuum by fans in the down-stream end of the plant, so the furnace gases moves past an electrostatic precipitator to remove dust and then to a water cooled condenser. Liquid yellow phosphorous is collected under water for further processing. CO (2.5-3 tons\tons P) is used as fuel or for synthesis gas after clean up. The mixture is fed to top of electric furnace.

MOLTEN SLAG

The Molten slag (8 tons\ton of P) from the bottom of the furnace is tapped periodically, cooled and crushed for road bed gravel, soil liming and glass manufacture. Where Ferro phosphorous 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 weighing agents in oil drilling(muds).

MAJOR ENGINEERING PROBLEMS

Electric

furnace design: High voltage with large reaction zone desirable to reduce the electrodes and transformer system for the same input. This saves money on power equipment and electrode purchases. Safety in handling P: Most of the yellow P is converted in to H3PO4. It is bulk shipped by tankage via boat, rail and truck. Water is kept over the top surface to avoid direct contact with air since yellow phosphorous oxidizes vigorously.

APPLICATIONS Phosphorus being an essential plant nutrient, finds its major use as a constituent of fertilizers for agriculture and farm production in the form of concentrated phosphoric acids, which can consist of 70% to 75% P2O5. Global demand for fertilizers led to large increase in phosphate (PO43-) production in the second half of the 20th century. Phosphorus is widely used to make organophosphorus compounds, through the intermediates phosphorus chlorides and the two phosphorus sulfides: phosphorus pentasulfide, and phosphorus sesquisulfide.[1] Organophosphorus compounds have many applications, including in plasticizers, flame retardants, pesticides, extraction agents, and water treatment.

APPLICATIONS
Phosphates are utilized in the making of special glasses that are used for sodium lamps. Bone-ash, calcium phosphate, is used in the production of fine china. Sodium tripolyphosphate made from phosphoric acid is used in laundry detergents in some countries, but banned for this use in others. Phosphoric acid made from elemental phosphorus is used in food applications such as some soda beverages. The acid is also a starting point to make food grade phosphates.[1] These include mono-calcium phosphate which is employed in baking powder and sodium tripolyphosphate and other sodium phosphates[1]. Among other uses these are used to improve the characteristics of processed meat and cheese. Others are used in toothpaste.[1] Trisodium phosphate is used in cleaning agents to soften water and for preventing pipe/boiler tube corrosion. White phosphorus is used in military applications as incendiary bombs, for smokescreening as smoke pots and smoke bombs, and in tracer ammunition. Red phosphorus is essential for manufacturing matchbook strikers, flares,[1] safety matches, pharmaceutical grade and street methamphetamine, and is used in cap gun caps. Phosphorus sesquisulfide is used in heads of strike-anywhere matches.[1] In trace amounts, phosphorus is used as a dopant for N-type semiconductors. 32P and 33P are used as radioactive tracers in biochemical laboratories (see Isotopes

MANUFACTURE OF H3PO4

Direct conversion at plant site

Phosphate Rock Fines Recycle Air

PRODUCTION OF H3PO4
ElectroStatic Precipitator

Sintener

Coke Breeze

Sand
250-300v 3 Phase AC Power

Fines To Waste`

CO
Ambient Air(Not Dried)
Electrostatic Demister

` 1400 C Slag Electric furnaces Air cooled

P4,CO,Dust
P2O5 Route

Combustion Chamber

H2O

H2SO4

Purified 85% H3PO4

Powdered SiO2

H2S

Crushed Slag

Sludg

Purification Process

STRUCTURE OF H3PO4

PHYSICAL PROPERTIES
Molecular formula Molar mass H3PO4 98.0 g/mol white solid or colorless, viscous liquid (>42C) 1.685 g/ml (liquid) 42.35 C, 316 K, 108 F 158 C, 431 K, 316 F (decomp.)

Appearance

Density Melting point Boiling point

Acidity (pKa)
Viscosity

2.12, 7.21, 12.67

85% aqueous solution

RAW MATERIALS

Crushed Phosphate rock Coke Sand H2SO4 H2O

CHEMICAL REACTIONS

2 Ca3(PO4)2 + 6 SiO2 + 10 C > P4 + 10 CO + 6 CaSiO3 P4 + 10 CO + 10 O2 > 2 P2O5 + 10 CO2 P2O5 + 2 CH2O > 2 H3PO4 + (x-3) H2O

PROCESS DESCRIPTION The first part of the electric furnace process is identical with that described under phosphorous until the vapors leave the furnace. The oxidation of these gases is accomplished by an air combustion section downstream section 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. The crude 85% acid is given an H2SO4 treatment to remove CaSo4,a powdered silica addition to remove HF and H2S to remove AsS3.The sludge is then removed.

MAJOR ENGINEERING PROBLEMS

Complete removal of acid mist:

By purely fluid mechanics designs, a system which includes Pease-Anthony scrubber, screens and final water spray has been successfully adopted.

Materials of construction:

High temperature acid brick is used in the furnace and combustion chamber areas. The electrostatic precipitator is graphite to resist the action of the free HF steel present.

APPLICATIONS

Phosphoric acid is used as the electrolyte in phosphoric-acid fuel cells. It is also used as an external standard for phosphorus-31 nuclear magnetic resonance (NMR). Phosphoric acid is used as a cleaner by construction trades to remove mineral deposits, cementitious smears, and hard water stains. It is also used as an ingredient in some household cleaners aimed at similar cleaning tasks. Hot phosphoric acid is used in microfabrication to etch silicon nitride (Si3N4). It is highly selective in etching Si3N4 instead of SiO2, silicon dioxide. [8]

APPLICATIONS
Phosphoric acid is used as a flux by hobbyists (such as model railroaders) as an aid to soldering. Phosphoric acid is also used in hydroponics pH solutions to lower the pH of nutrient solutions. While other types of acids can be used, phosphorus is a nutrient used by plants, especially during flowering, making phosphoric acid particularly desirable. General Hydroponics pH Down liquid solution contains phosphoric acid in addition to citric acid and ammonium bisulfate with buffers to maintain a stable pH in the nutrient reservoir. Phosphoric acid is used as a pH adjuster in cosmetics and skin-care products.[9] Phosphoric acid is used as a chemical oxidizing agent for activated carbon production.[10] Phosphoric acid is also used for High Pressure Liquid Chromotography.

MANUFACTURE OF H3PO4

OXIDATION AND HYDRATION OF ELEMENTAL PROCESS

RAW MATERIALS

Elemental phosphorous Steam Air

CHEMICAL REACTIONS

2 P + 2 H20 > P2O5 P2O5 + 3 H2O > 2 H3PO4

PROCESS DESCRIPTION Phosphorous is melted at 50C and metered by water displacement to a steam ejector and atomization section of the combustion nozzle. Compressed air is injected around steam atomized phosphorous droplets and the exothermic reaction rises the gas temperature to 2000C.the entire chamber is about 1.2m diameter and 3m long and is built of stainless steel with water cooled walls. The gaseous oxides, partially hydrated, are treated for conversion of electric furnace gas to 85%H3PO4.

MAJOR ENGINEERING PROBLEMS

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 clean out. By placing the combustion chamber near the bottom a great deal of the metaphosphoric acid can be vaporized and passed overhead.

APPLICATIONS
Metal finishing

Chemical manufacture

Phophatizing compounds for rustproofing,as the major ingredient in solutions used for the chemical & electrochemical polishing of aluminium,stainless steel & copper alloys. Production of phosphate salts

Equipment maintenance
Ceramics & Glass Plastics Drinking water treatment

Descaling of boilers and heat exchanger tubes

Petroleum polymerization of propylene ; alkylating catalyst. As catalyst to speed up setting action of some synthetic resins. Food grade acid used for corrosion control

A PRESENTATION BY

VIRUDHAGIRI.M VINOTHRAJ.M TAMILSELVAM SORNALINGAM.M BABU KANNAN DEEPAK KUMAR YUVANASHREE.E SURYAKALA.M SINDHUJA.S SINDU.S