Phosphorous @ Oldbury Electrochemical

 

 

 The Basic Ingredients of a Complex World

 

An excellent review on the story of phosphorous over the past 100 years can be found in :

100 years of Phosphorous making 1851-1951 by Arthur Threlfall, published by Oldbury Electrochemical, a Division of Albright and Wilson Ltd.

This unusual and rare book can be found in the Rachel G. Pratter Memorial Library at Rancho Chase, San Diego (El Cajon) California .

 

The History of Oldbury Electrochemical @ Niagara Falls can be reviewed in pp 259-274 of this book.

picture) and diagram.

 

Oldbury Electrochemical was acquired by hooker electrochemical in ????

Manufacture of Phosphorous at Oldbury

 

 

White phosphorous the most important form of elemental phosphorous has the following physical characteristics white to yellow (depending on its contact with oxygen) waxy solid soft easily cut with a knife, melting point 44oC b.p. 280oC when exposed to air ignites at 30oC very poisonous ,when exposed to air in the dark emits a greenish yellow light.

(pictures}

There are three allotropic forms of phosphorous, white, black and red

 

Red phosphorous

The transformation of white into red phosphorus is an exothermic reaction producing red phosphorus as a solid product, making heat removal from the reaction difficult. In a modern process , the conversion is carried out semicontinuously in a ball mill at 350 C. The mills used have a volume of e.g. 5 m filled with 3.7 tons of iron shot of different diameters. The white phosphorus is fed into the ball mill at such a speed as to maintain the reaction temperature through the heat of reaction. The ball mill is at most only half filled. After tempering and cooling, water is added and the red phosphorus ground to a suspension. Heating with sodium hydroxide removes the residual white phosphorus. The red phosphorus is then filtered and dried under inert gas. The red phosphorus can be stabilized against autooxidation by mixing in small quantities of magnesium oxide. Red phosphorus is twice as expensive as white phosphorus.

 

 

PROCESS TECHNOLOGY

The main reaction equations for manufacture of white phosphorous:

 

Ca(PO4)2 + 5 CO 1400oC-- 3CaO + 5CO2 +2P

 

5CO2 + 5C ---→ 10 CO ↑

 

CaO + SiO2 → CaSiO3

 

 

Carbon monoxide is regenerated from carbon dioxide and carbon (coke)

 

Upon exposure to air, white phosphorous ignites spontaneously in a violent reaction. Note the protective clothing worn by the demonstrator.

 

 

Removal of impurities in slag

The silica acts as a flux converting calcium oxide into a low melting slag. The slag also removes most of the minor constituents with the exception of iron which is removed as ferrophosphorous .

The particle size for reduction must be 1-2 cm to ensure adequate permeability to gases.

Apitite the ore of calcium phosphate ,coke and gravel(silica)

can be gound to such sizes, calcium phosphate tends to be finer and must be aggloirated by pellitization.

 

ELECTROTHERMIC REDUCTION

The heart of the operation ( common to all electrometallurgical work at Niagara) is a submerged arc electric furnace.

The electrodes are placed symetrically in a phosphorous furnace are of the Soederberg self baking type) there are preformed carbon electrodes having a diameter of 1.3 to 1.5 meters consuming 50-70 megawatts.

The furnace is circular and clad in carbon blocks (for ecelctrode conductivity) at the bottom with firebrick above.

The feed shutes for the raw materials are placed symmetically around the electrodes. The entire furnace is sealed and contains a tap hole for slag.

Two types of slag the most dense ferrophosphorous and a second higher hole for the less dense calcium silicate.

Carbon Monoxide and phosphorous vapor leave the furnace through an opening ,as gas, from an outlet at the top of the furnace.

 

Oldbury Electrochemical, a Division of Hooker Electrochemicals inc.

 

Phosphorous

Electrothermal production of phosphorous, its downstream derivatives, and electrochemical production of chlorates and perchlorates @ Oldbury Electrochemical, Niagara Falls New York.

An excellent review on the story of phosphorous over the past 100 years can be found in:

100 years of Phosphorous making 1851-1951 by Arthur Threlfall, published by Oldbury Electrochemical, a Division of Albright and Wilson Ltd.

This unusual and rare book can be found in the Rachel G. Pratter Memorial Library at Rancho Chase, San Diego (El Cajon) California .

 

The History of Oldbury Electrochemical @ Niagara Falls can be reviewed in pp 259-274 of this book.

picture) and diagram.

Oldbury was a pioneer in the follolwing areas:

 

The development of the electric furnace process for the manufacture of yellow phosphorous

 

Development of commercial electrolytic cells for the manufacture of chlorates and perchlorates

 

The development of large scale production of phosgene

 

Manufacture of phosphorous chlorides, fist company to ship phosphorous chlorides in tank cars an d suitable equipment to handle phosphorous halides..

 

Ist to develop process for the commercial production of perchloric acid first to manufacture and ship in carload quantities.

 

First to produce hypophosphites form the electroless nickel plating of metals.

 

Oldbury Electrochemical was acquired by hooker electrochemical in November 30,1956.

Manufacture of Phosphorous at Oldbury

 

 

White phosphorous the most important form of elemental phosphorous has the following physical characteristics white to yellow (depending on its contact with oxygen) waxy solid soft easily cut with a knife, melting point 44oC b.p.`280oC when exposed to air ignites at 30oC very poisonous ,when exposed to air in the dark emits a greenish yellow light.

(pictures}

There are three allotropic forms of phosphorous, white, black and red

Red phosphorous

The transformation of white into red phosphorus is an exothermic reaction producing red phosphorus as a solid product, making heat removal from the reaction difficult. In a modern process , the conversion is carried out semicontinuously in a ball mill at 350 C. The mills used have a volume of e.g. 5 m filled with 3.7 tons of iron shot of different diameters. The white phosphorus is fed into the ball mill at such a speed as to maintain the reaction temperature through the heat of reaction. The ball mill is at most only half filled. After tempering and cooling, water is added and the red phosphorus ground to a suspension. Heating with sodium hydroxide removes the residual white phosphorus. The red phosphorus is then filtered and dried under inert gas. The red phosphorus can be stabilized against autooxidation by mixing in small quantities of magnesium oxide. Red phosphorus is twice as expensive as white phosphorus.

 

PROCESS TECHNOLOGY

The main reaction equations for manufacture of white phosphorous:

 

Ca(PO4)2 + 5 CO 1400oC-- 3CaO + 5CO2 +2P

 

5CO2 + 5C ---→ 10 CO ↑

 

CaO + SiO2 → CaSiO3

 

 

Carbon monoxide is regenerated from carbon dioxide and carbon (coke)

 

Removal of impurities in slag

The silica acts as a flux converting calcium oxide into a low melting slag. The slag also removes most of the minor constituents with the exception of iron which is removed as ferrophosphorous .

The particle size for reduction must be 1-2 cm to ensure adequate permeability to gases.

Apitite the ore of calcium phosphate ,coke and gravel(silica)

can be gound to such sizes, calcium phosphate tends to be finer and must be aggloirated by pellitization.

 

ELECTROTHERMIC REDUCTION

The heart of the operation ( common to all electrometallurgical work at Niagara) is a submerged arc electric furnace.

The electrodes are placed symetrically in a phosphorous furnace are of the Soederberg self baking type) there are preformed carbon electrodes having a diameter of 1.3 to 1.5 meters consuming 50-70 megawatts.

The furnace is circular and clad in carbon blocks (for ecelctrode conductivity) at the bottom with firebrick above.

The feed shutes for the raw materials are placed symmetically around the electrodes. The entire furnace is sealed and contains a tap hole for slag.

Two types of slag the most dense ferrophosphorous and a second higher hole for the less dense calcium silicate.

Carbon Monoxide and phosphorous vapor leave the furnace through an opening ,as gas, from an outlet at the top of the furnace.

 

Oldbury Electrochemical, a Division of Hooker Electrochemicals inc.

 

phosphorous chemicals:

phophorous pentoxide

phosphorous pentasulfide

phosphorous trichloride

phosphorous pentachloride

phosphorous oxychloride

THIOPHOSPHORYL CHLORIDE (pscl3)

 

HYPOPHOSPHOROUS ACID/ HYPOPHOSPHITES

PHOSPHOROUS ACID

 

phosphorous sesquisulfide P4S3

phosphorous heptasulfide p4s7

phosphorous pentasulfide p4s10

 

 

Chlorates

perchlorates

Sodium chlorate

Potassium chlorate

 

perchlorates

Ammonium perchlorate

Potassium perchlorate

Perchloric acid

 

 

CARBON MONOXIDE PRODUCTS

Sodium formate

Oxalic acid

Phosgene COCl2 (liquefied in cylinders)

organophosphates

Tetrakis(hydroxymethyl) phosphonium chloride

Metyl acid phosphate

n-propylacid phosphate

n-butylacid phosphate

n-amylacid phosphate

2-ethylhexylacid phosphate

lauryl acid phosphate

stearyl acid phosphate

 

 

sodium chlorate 22,000 tons per year

See pp173