Phosphoric Acid, Phosphates & Fertilizers Experts

Phosphoric Acid History

Hennig Brand(t) (c. 1630 – c. 1710) was a merchant and alchemist in Hamburg, Germany who discovered phosphorus around 1669. Like other alchemists of the time, Brand searched for the "philosopher's stone", a substance which purportedly transformed base metals (like lead) into gold. By the time his first wife died he had exhausted her money on this pursuit. He then married his second wife Margaretha, a wealthy widow whose financial resources allowed him to continue the search. Like many before him, he was interested in water (H2O) and tried combining it with various other materials, in hundreds of combinations. He had seen for instance a recipe in a book 400 Auserlensene Chemische Process by F. T. Kessler of Strasbourg for using alum, saltpetre (potassium nitrate) and concentrated urine to turn base metals into silver (a recipe which of course didn't work). Around 1669 he heated residues from boiled-down urine on his furnace until the retort was red hot, where all of a sudden glowing fumes filled it and liquid dripped out, bursting into flames. He could catch the liquid in a jar and cover it, where it solidified and continued to give off a pale-green glow. What he collected was phosphorus, which he named from the Greek for "light-bearing" or "light-bearer." Phosphorus must have been awe-inspiring to an alchemist. A product of man, and seeming to glow with a life force that didn't diminish over time (and didn't need re-exposure to light like previously discovered Bologna stone). Brand kept his discovery secret, again as alchemists of the time did, and worked with the phosphorus trying to use it to produce gold (unsuccessfully of course).

Boil urine to reduce it to a thick syrup.

Heat until a red oil distills up from it, and draw that off.

Allow the remainder to cool, where it consists of a black spongy upper part and a salty lower part.

Discard the salt, mix the red oil back into the black material.

Heat that mixture strongly for 16 hours.

First white fumes come off, then an oil, then phosphorus.

The phosphorus may be passed into cold water to solidify.

The chemical reaction Brand stumbled on was as follows. Urine contains phosphates PO43-, as sodium phosphate (ie. with Na+), and various carbon-based organics. Under strong heat the oxygen from the phosphate react with carbon to produce carbon monoxide CO, leaving elemental phosphorus P, which comes off as a gas. Phosphorus condenses to a liquid below about 280°C and then solidifies (to the white phosphorus allotrope) below about 44°C (depending on purity). This same essential reaction is still used today (but with mined phosphate ores, coke for carbon, and electric furnaces). The phosphorus Brand's process yielded was far less than it could have been. The salt part he discarded contained most of the phosphate. He used about 5,500 litres of urine to produce just 120 grams of phosphorus. If he'd ground up the entire residue he could have got 10 times or 100 times more (1 litre of adult human urine contains about 1.4g phosphorus). Phosphoric acid was discovered in 1770 by K. W. Scheele and J. G. Gahn in bone ash . Scheele later isolated phosphorus from bone ash (1774) and produced phosphoric acid by the action of nitric acid on phosphorus (1777). In Lyon, Coignet & Cie, founded in 1818 to manufacture gelatin and glue by treating bone with hydrochloric acid became the leading French manufacturer of pure phosphorus and a major manufacturer of matches until the latter became a government monopoly in 1872; thereafter Coignet concentrated on making superphosphates from bonemeal as well as copper phosphate, phosphoric acid and phosphate of soda. The initial interest in manufacturing phosphoric acid for fertilizers probably seems from Justus Von Liebig's significant book entitled Organic Chemistry in its Application to Agriculture and Physiology (1840). In this book Liebig stated that the insoluble phosphate present in bones and mineral phosphate, through treatment with sulfuric acid, could be converted to a form that served as a nutrient to growing plants [1]. John Bennet Lawes was an English entrepreneur and agricultural scientist. He founded an experimental farm at Rothashed, where he developed a superphosphate that would mark the beginnings of the chemical fertilizer industry. In 1832, Lawes had begun to interest himself in growing various medicinal plants on the Rothamsted estates, which he inherited on his father's death in 1822. About 1837 he began to experiment on the effects of various manures on plants growing in pots, and a year or two later the experiments were extended to crops in the field. One immediate consequence was that in 1842 he patented a manure formed by treating phosphates with sulphuric acid, and thus initiated the artificial manure industry. In the succeeding year he enlisted the services of Joseph Henry Gilbert, with whom he carried on for more than half a century those experiments in raising crops and feeding animals which have rendered Rothamsted famous in the eyes of scientific agriculturists all over the world. Some 9 years later, Albright and Wilson, Ltd was founded at Oldbury.In the early days, white phosphorus was obtained from bone ash by treating them with hydrochloric acid to produce precipitated phosphates. Then heating the meta phosphate for several days in a sealed crucible, in a retort, and distilling off phosphorus vapour, under water. Huge quantities of coal were needed for heating these retorts. The production of white phosphorus was improved by using phosphate rock and sulfuric acid instead of bone ash and hydrochloric acid; and by the use of reverberatory furnaces instead of the direct-heated furnaces. White and amorphous phosphorus remained the main product of Albright and Wilson until World War I. White phosphorus was poisonous to match makers, causing Phossy jaw. Albright and Wilson exhibited amorphous phosphorus at the Great Exhibition of 1851, at The Crystal Palace. A sample was taken away for testing by the two Swedish brothers Lundstrom, to make an experimental match composition. In 1855, just before the Paris Exhibition, John Edvard Lundstrom found that the matches were still usable. He placed a large order for amorphous phosphorus with Albright and Wilson and this led to the foundation of the Swedish Safety Match Industry. In 1899 Albright and Wilson added phosphorus sesquisulfide production. They were the first company to produce phosphorus sesquisulfide commercially: it was fiery and dangerous to make. Two French chemists, Savene and Cahen, proved that year that it was non-poisonous and could be used to make safety matches. Savene and Cahen Patented the match formula. In 1929 the British Match Corporation, formerly known as Bryant and May, set up a jointly-owned company with Albright and Wilson: The A & W Match Phosphorus Company. It took over ownership of a small part of the Oldbury site concerned with producing amorphous phosphorus and phosphorus sesquisulfide. In 1955 Albright and Wilson took over the Marchon Chemical Company based in Whitehaven, which produced phosphorus-based detergents by the "wet" process. The A&W Group now controlled production of phosphorus compounds by both important manufacturing routes. However, the phosphate detergent business, which was the bread-and-butter market for Marchon, ran into terminal decline in the late 1970s as the eutrophication of inland waterways by pollution from detergent phosphate residues pressed the detergent formulators to move away from phosphates, thus removing Marchon's prime product application area. The name "Marchon" ended when the French company, Rhodia, took over Albright and Wilson in 1999. Phosphorus was made in the United States in 1897 by the Oldbury Electrochemical Company at niagara Falls, New York. The plant of the American branch of the English Company, Albright and Wilson of Oldbury, was located at the upper end of Power Company land. It used 1,000 hp. to make 1,000 pounds of electric furnace yellow phosphorus and 1,000 pounds of potassium chlorate per day. Sodium chlorate and perchlorate were soon added. Phosphorus was produced in six electric furnaces of 50 hp. each using phosphate ore mixed with carbon and sand. Phosphorus distilled from the furnace was condensed under water. A calcium silicate slag was tapped out periodically. While platinum anodes were used originally in the chlorate cells, graphite anodes were adapted soon after they became available. This company would also become part of the Hooker Chemicals and Plastics Company. Hooker Electrochemical Company acquired Oldbury Chemical Company in 1956, and Niagara Alkali Company in 1957. Hooker was acquired by Occidental Petroleum Corporation in 1968, and was renamed Occidental Chemical Corporation in 1983. Fertilizer activity of Oxy was acquired in 1995 by Potash Corp (PCS). Among the pioneers in wet-process phosphoric acid was the Stauffer Chemical Company, where a process was developed in 1897 for acidulating bones from the Chicago stockyards to make acid for use in the manufacture of calcium leavening agents [1]. Among the several large industrial chemical factories established in the area during the early twentieth century, only some were owned by local interests. One of the home-grown operations was the Victor Chemical Works, which was started by the German-born August Kochs in 1902. Kochs, who for several years had been experimenting with the manufacture of baking powder, directed the production of monocalcium phosphate at the Victor plant in Chicago Heights. By the 1910s, Victor was making ammonium phosphate and sulfuric acid. By the 1960s, the company (then controlled by the Stauffer Chemical Company) employed more than 1,000 Chicagoans. Stauffer was later acquired by Rhône Poulenc from France and becomes today Innophos. Another early producer was American Agricultural Chemical Company, which began operating a plant in 1902 in conjunction with phosphate chemicals manufacture at Carteret, New Jersey [1]. The Dorr Company developed an airlift agitation system. American Agricultural Chemical Company (AGRICO) As the bone industry grew, one manufacturing site did too. This site was located in the Detroit area, Michigan Carbon Works. Michigan Carbon Works was established in 1873 by Deming Jarves and William Hooper. The main objective of Michigan Carbon Works was the destructive distillation of bones into animal charcoal to meet the growing demands of the sugar industry for filtering and purifying sugar. Jarves and Hooper began their business with $18,000 capital investment and a building in Hamtramck, Michigan. Initially, only bone charcoal was produced. Being enterprising men, their stock products were expanded to include glues, fertilizer, neat’s foot oil and other compounds related to bones. Business grew so quickly, that by 1879 the Michigan Carbon Works needed room to expand. In 1880, Michigan Carbon Works bought the Harbaugh Farm in Springwells. This consisted of 72 acres near the Rouge River near Delray, Michigan. A sprawling complex, nicknamed "Boneville" was to emerge. A complex with 5 acres of floor space, costing $100,000 was built. Along with this, a boarding house on Forman Street to house 60 single employees, and 25 duplex cottages on Carbon Street for married workers. By 1883, Michigan Carbon Works became the most extensive and complete carbon works in the United States. Business was doing so well, that by 1885, the company was conducting over $50,000 worth of business per month. Bone charcoal was being produced on a 24 hour basis, using approximately 13% of bison bones from the prairies, one of the largest places of consumption in the country. By 1892, Michigan Carbon Works was the largest industry in Detroit. The plant covered 100 acres, employed 750 people, and had 10 acres of facilities that included a 50 building complex. Two buildings and a tower housed the sulfuric acid works, with a 30 ton per day capacity. A muriatic acid plant connected to the gelatin works plant by an overhead pipeline. Buildings housed four different gelatin factories, each devoted to a special line of gelatin. Ten buildings were devoted to the manufacture of homestead fertilizers, and beyond these, were the bone black works. As the bone crisis on the prairies developed, Michigan Carbon Works began stockpiling bones. By 1896, nearly all buffalo bones were cleared from the Plains. Due to the foresight of this company, Michigan Carbon Works survived, using alternate sources of raw materials. Fertilizers made from bones, due to the scarcity and cost of bones, needed to find substitute materials. Most companies substituted phosphate rock and other cheaper materials for soil dressings. Michigan Carbon Works through its animal charcoal production, created a large component of phosphorous rich bone black dust that was too fine for the sugar industry. Instead of selling this dust, at this point, it was used as a basis for their homestead fertilizer. Bone char and dust production continued well into the 1920’s when American Agricultural Chemical Company (Agrico) began consolidating bone char producing Companies. Michigan Carbon Works became a division of Agrico, as well as Cornelieus Harold Tiers (Philadelphia), Lister’s Agricultural Chemical Works (Newark), and Empire Carbon Work’s (St. Louis). Bone char dust became known as bone black pigment and continued to grow in the pigment industry. Its uses varied from India ink to mascara for cosmetics, and paints and varnishes. Bone black became one the major black colorants. At the turn of the century, a new industry began to make its mark on the economy - oil. As the industry grew, one of its many by-products was a substance called carbon black, a black tinting pigment. At first it was thrown away, then given away. When oil companies found there was a demand for it, they began charging a nominal price for it. With the available supplies of carbon black at a cheap price, bone black was nearly forgotten except for a few applications where its superior handling properties and other advantages made it worth the extra cost. Then came the oil shortage and the rapid rise in the prices of all products derived from oil, including carbon black. During the 1960’s, American Agricultural Company (Agrico) was pulling out of the Detroit area and was selling off divisions originally started by the Michigan Carbon Works. The bone black division was one of them. The division was purchased, and the Ebonex Corporation was formed. Dorr John Van Nostrand Dorr (1872 - 1962) invented many devices that greatly increased the efficiency of the cyanide method of gold extraction and were later applied to other industries. Dorr began his career in the laboratories of Thomas Edison. Later, while working as an assayer and metallurgist in the gold mills of South Dakota and Colorado he invented the Dorr Classifier. Although the Classifier was initially used for the continuous extraction of gold by the cyanide process, its use rapidly spread to many industries. Of the more than 20 patents awarded him, the most important include: the Dorr Thickener: for the continuous thickening of ore slurry, and the Dorr Air-Lift Agitator; for the continuous mixing of liquids. These 3 inventions had a huge impact on the processing of mining materials by hastening the transition from intermittent to continuous processing. Later the Dorr Thickener became a basic tool used in water and sewage treatment plants and the sedimentation processes he invented rendered economically feasible the desilting of water from the Colorado River for use in irrigating California's rich Imperial Valley. [1] PHOSPHORIC ACID Part 1 edited by A. V. SLACK 1968 Marcel Dekker Inc, New York