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A Short History of Fertilisers
H LS Tandon
Director
Fertiliser Development and Consultation Organisation
204-204 A, Bhanot Corner, Pamposh Enclave
New Delhi 110048 (INDIA)
fdco@ airtelmail.in (www.tandontech.net),

Note: This paper, one of over 120 paper written by Dr Tandon,  was published in the Indian Journal of Fertilisers, 2010. It was a revised and updated version of the paper prepared for the souvenir of the Indian Society of Soil Science on the occasion of its Platinum Jubille in December 2009.

Introduction

The advent of chemical/mineral fertilizers is a post 1800 development. This paper provides a brief history of chemical/mineral fertilizers without going into how our ancestors went about various ways of improving soil fertility starting as far back as 4,500 years ago (18). By and large, the history of fertilizers and their development revolves around the discovery and invention of some key materials/processes. These concern industrial nitrogen fixation into ammonia, search for suitable catalysts, urea synthesis, sulphur, phosphate rock, potash minerals, sulphuric acid and phosphoric acid. The major contributions were those of Liebig, Lawes, Haber, Bosch, Wohler, Johansen and  Frasch. Foundations of the fertilizer industry were laid primarily in Germany, Norway, UK and North America. Over the years, fertilisers, the end product of their efforts have benefited billions of people not once or twice but on a sustained basis and will continue to do so. A more detailed account of the subject including also the developments related to agriculture and plant nutrition is available in several publications (1,3,7,10,16,21, 22,24).

The Starting Point - Chilean Nitrate

The first known mineral fertilizer was sodium nitrate (16% N), also known as nitrate of soda or Chilean nitrate. It is considered as the first natural mineral   containing fixed N and , the only natural source of nitrate N. Although its deposits were found in several countries, the source of real commercial significance was found in north Chile (South America), hence the name Chilean nitrate. First commercial mining of this material was done in the early 19th century by the Spaniards. It was imported into Europe and America around 1830. Synthetic sodium nitrate was first produced in 1928 in the US. Now it can also be manufactured through one of several processes. At present, it is a fertilizer of small, localised and special applications but it is still used as a standard against which the salt index of various fertilizers is measured. Its salt index is taken as 100.

Birth of the Phosphates – Enter Bone meal, SSP and Basic Slag

Crushed bones were one of the first P-rich materials to be used as a phosphatic fertilizer. Justus von Liebig of Germany  treated powdered bones with sulphuric acid and found them to be more effective than untreated bones. When phosphate rock was not discovered, most probably, crushed bones were used to acidulate to produce SSP in the mid 1840s.An interesting account of the discoveries and development of phosphate industry has been provided by Hall (7) exactly a century ago. Historically, there were four main players in the development of phosphate fertilizers. They were Liebig of Germany, Lawes and Henslow of U.K. and Murray of Ireland.

Superphospate:

Liebig was the first person to point out in 1840 that sulphuric acid added to ground bones gave a form of phosphate which was more quickly available to plants than raw bones. He is generally regarded as the inventor of single super phosphate (SSP), but James Murray of Dublin, Ireland can also take the credit for doing so.

It is generally accepted that  John Bennet Lawes was the first person to make the manufacture of a fertilizer, in this case SSP(mono calcium phosphate with gypsum Ca CaH2PO4.CaSO4) a practical possibility. He took out a patent 1n 1842 for treating mineral phosphates with sulphuric acid. However, it seems that Sir James Murray of Ireland was the first one who produced a fertilizer in 1808, many years ahead of Lawes. His process was based on the acidulation of phosphorite (a rock consisting chiefly of calcium phosphate) with sulphuric acid. The first product he made was a liquid but followed it up with a solid fertilizer. Later, Lawes purchased Murray’s patent to get any competition out of the way and amended it. Lawes’s first product consisted of solid and insoluble phosphates derived from coprolites or guano mixed with animal remains. It resembled a product which was described as soluble bones at that time.

Soon after, in 1845, Prof Henslow discovered the beds of coprolite near Cambridge, UK. These consisted of small roundish nodules of impure calcium phosphate mixed with bones, shell and teeth of sharks etc. These contained about 60 percent calcium phosphate, 10 percent calcium carbonate and 3 percent calcium fluoride.  The dictionary meaning of coprolite is “a stony roundish fossil, the petrified excrement of a vertebrate” (2). The quantities mined were almost wholly used to manufacture SSP.First superphosphate plant complete with a  sulphuric acid production facility was built in 1854 by Packard at Ipswich, England.  SSP was also the first fertilizer to be manufactured in India, in 1906, at Ranipet in Tamil Nadu.

Basic Slag:

In 1877, S G. Thomas, a British engineer developed the process in which steel was made using P-rich iron minerals (24). During the process, by-product slag (containing lime and phosphate ) was formed which  after solidification and cooling, could be used to fertilise acid soils. Thus basic slag or Thomas slag as it was popularly called, came into being. Thomas slag became a very popular fertilizer in many parts of Europe
 

Urea[CO(NH2)2] - The First Organic Compound Synthesized

Urea was the first organic compound to be synthesized from inorganic materials.  It was first separated from urine by Rouelle in 1773, hence the name urea. In 1782, Prout separated pure crystalline urea. It was first synthesized by Friedrich Wohler (1800-1882) of Germany in 1828 by heating ammonium cyanate (4). According to another source (23), urea was first synthesized by reacting ammonia with cyanuric acid. In any case, the synthesis of urea by Wohler revolutionized the chemical technology scene in general and the fertilizer scene in particular to such an extent that he himself may not have expected. Commercial production of urea had to wait until 1922 after the large scale synthesis of ammonia was made possible by Fritz Haber (1868-1934) and Carl Bosch in 1910. The I.G. Farbenindustrie in Germany was the first company to synthesise urea commercially from ammonium carbamate 1n 1920. In 1922, large scale production of urea by the BASF process started. Urea now dominates the N fertilizer scene. In India, the first urea plant was set up in 1959 at Sindri in Bihar. In India close to 27 million tones urea was consumed during 2008-2009 accounting for 82% of total fertilizer N (6).

Ammonia Synthesis

Ammonia gas was first produced by J. Priestly in 1754 by distilling ammonium chloride with quick lime. Although, Ammonium Sulphate (NH4(SO4)2 arrived on the scene in the later half of 19th century as a by product of the coke oven industry, synthesis of ammonia had to wait. By 1905, the idea of passing air through an electric arc was successfully developed in Norway to produce nitric acid. The path-breaking synthesis of ammonia in a reactor was achieved by two Germans Fritz Haber and Carl Bosch in 1910. The key link in ammonia synthesis was the search for a suitable and easily available catalyst. One of Bosch’s colleagues was fortunate to find that red iron oxide was as good as the scarcely available osmium. In recognition of their contribution, Haber was awarded the Nobel Prize in 1918 and Bosch in 1931. In his acceptance speech at the Nobel Prize award ceremony, Carl Bosch disclosed that more than 20,000 experiments were needed to develop a useful catalyst for industrial use (21).

The first commercial plant for ammonia synthesis began operation in 1913 by BASF AG at Ludwigshafen-Oppau in Germany. Soon it yielded 30 tonnes of fixed N/day. This period and development can be considered as the starting point for large scale production of a variety of concentrated  fertilizers containing nitrogen alone as in urea or an array of NP/NPK materials.

Anhydrous Ammonia and Nitrogen Fertilisers

 solid and liquid fertilizers, it also emerged as an important N fertilizer on its own. Anhydrous ammonia was first applied directly in the field on a commercial scale in the United States during1943-44. Its diluted form “aqua ammonia” (ammonium hydroxide) which found use in fluid fertilizers. Although registered as a fertilizer in the FCO, anhydrous ammonia is rarely used for direct application in India.

Ammonium Sulphate (AS):

It was the first nitrogenous fertilizer to be produced, first as a by product of the manufacture of coal gas in 1815 in England and later from coke-oven battery gas (3). It thus appears to have preceded single superphosphate as the first synthetically produced fertilizer. Its production as a by product gained importance in the later half of the 19th century in Europe and then in the USA in 1893.   Ammonium  sulphate was first produced in India in 1933 (at Jamshedpur in Jharkhand) as a bi-product of the steel industry followed its manufacture using sulphuric acid in 1941 (at Belagula in Karnataka), using gypsum as a raw material in 1947( at Ugyogamandal, Kerala) and as a bi-product of the polymer (caprolactum) industry in 1974( at Vadodara in Gujarat).

Calcium Cyanamide:

A mention must be made of calcium cyanamide/cyan amide (CaCN2) which found use as an N fertilizer without taking the ammonia route. It was first synthesized by Frank and Caro in Germany in 1898 by reacting calcium carbide with N at high temperature (21). First commercial facility for its production was set up in Italy in 1905 and its production in the US started in 1910 (3). Its production reached 14,000 tonnes per year by the end of 1930s (24). With 21% N, it became a popular fertilizer for many years in the west.

Ammonium Nitrate and Calcium Ammonium Nitrate:

The production of ammonium nitrate started in Europe after the commercial production of ammonia was made possible. A potential explosive, its first use as a fertilizer was in Europe after World War I when the war surplus material was released for other uses. Later on, to eliminate any possibilities of the hazard due to its explosion when in contact with organic materials or other unfavorable conditions, it was mixed/diluted with limestone to produce calcium ammonium nitrate (CAN). This also brought down the N content in the finished fertiliser from 33% in AN to 20-26% in CAN. In India, the production of CAN started in 1961 at Nangal, Punjab using electrolysis of water to produce H for ammonia synthesis. It was most popular in Europe and for a considerable period and  also in India.
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Sulphur and S-based fertilizers


Sulphur is a vital, rather indispensable raw material for the production of sulphuric acid which enabled the production of a large number of fertilizers. Sulphuric acid is perhaps the most widely used chemical in the world. Until the beginning of the 19th century, sulphur was used primarily as a component of gun powder. Over the last 200 years, its main use has been to to produce sulphuric acid.(11).
Elemental sulphur has been historically known as Brimstone. It can be a mined material or recovered from sour oil and gas. Marketable elemental S was first  produced in 1894 in Sulphur, Louisiana, USA. The most important process for mining of sulphur was the hot water process invented by Herman Frasch (1851–1914). Elemental S was recovered from the large sulphur mines in Texas and Louisiana states of the USA by the Frasch process around 1895. At present, considerable tonnage of sulphur is being recovered from oilaand gas   deposits.
Apart from use as a raw material for the production of sulphuric acid, fertilizers based on elemental S have also been developed and are being marketed in several countries, including India. One such product is sulphur bentonite or bentonite-containing 90% S in elemental form. Commercial sulphur bentonite mixtures were first marketed in the USA during the 1960s, a water degradable product containing 90% S granulated with bentonite clay is most widely used in various forms (direct application, bulk blends, suspensions).

Phosphate Rock – The Natural Non-Renewable Source of P

Phosphate rock (RP) or rock phosphate (PR) is the main source of phosphorus in fertilizers. First deposits of phosphate rock were discovered in the early 19th century and the first commercial development (mining) started in 1867 in South Carolina, USA. Later, in 1881, the Florida rock phosphates were discovered, followed by Tennessee rock phosphates in 1984. Sheldon (17) however provides a somewhat different account of the discoveries or rock phosphate deposits around the world. According to him, deposits were discovered in Palabora, S Africa around 1910 followed by Aulad Abdoun, Morocco close to 1920, on shore North Carolina, USA around 1950 etc. He makes no mention of the pre-1900 discoveries mentioned by Sauchelli (15).

There are differences in the dates regarding the discovery and mining of various phosphate rocks. According to Beaton (3), mining of phosphate rock started in the mid 1840s in Europe and in 1867 in South Carolina, USA (about 30 years after these were discovered). Mining of the famous Florida rock (discovered in 1873) started in 1889, about the same time as in Algeria and Tunisia. The discovery of Gafsa rock can be credited to Adolphe Carnot of Paris  who analysed the samples of “soil” sent to him by one  Philip Thomas, a British veterinarian who was serving in Tunisia.  Mining of Moroccan phosphate rock (discovered in 1914) started in 1921.

 Phospate rock, a non-renewable natural resource is the principal raw material for the production of phosphatic fertilizers the world over. In India, major deposits of phosphate rock were discovered in the1960s at Jhamarkotra in Rajasthan.
 
Rock phosphate was first used for direct application more than 150 years ago implying that the use of rock-P as a fertilizer is close to 200 years old. Research on rock phosphate for direct application as a fertilizer started over 100 years ago (20).

Partially acidulated phosphate rocks (PAPR) were first developed about 50 years ago and found extensive use in Europe and south  America. The idea behind PAPR development was to economise on the use of acid for fully solubilising phosphate rock and also in response to a view that complete acidulation (as in the case of SSP/TSP) may not be needed for all soils and crops.

Potassium Fertilisers

Potassium chloride (KCl) or muriate of potash (MOP) was the first potash fertilizer to be produced from mined material in Germany.. The word muriate is derived from muriatic acid (earlier name of hydrochloric acid). The German potash deposits are considered to have formed about 230 million years ago. Potash was mined for the first time in 1856 in Strassfurt, Germany and Germany was virtually the only potash producer until 1918 (8). Other potassium fertilizers such as potassium sulphate were manufactured later. Potassium Schoenite (K2SO4.MgSO4.6H2O) was recovered from sea bitterns on the west coast about 50 years ago. It contains 22-25% K2O ,8-10% MgO and 16%S. Its production has not made much progress. A somewhat   similar fertilizer, potassium magnesium sulphate consisting of the mineral langbenite (K2SO4.2MgSO4) is  mined in New Mexico, USA. It typically contains 22% K2O, 11% Mg , 22% S and 1.5% Cl. It is being imported and marketed in India. In India, no potash is produced and MOP accounts for over 99% of K consumption.

Gateways to Concentrated Fertilisers - Phosphoric Acid and Super Phosphoric Acid

The synthesis of phosphoric acid (H3PO4) in the USA paved the way for the production of highly concentrated phosphates such as triple superphosphate, DAP and polyphosphates etc. Wet process phosphoric acid is produced by treating phosphate rock with sulphuric acid.  In the process, 5-6 tonnes of by product phospho-gypsum is generated per tonne of P2O5. Phosphoric acid is used to produce not only TSP but ammonium phosphates, super phosphoric acid (76% P2O5), and fluid fertilizers. Triple super phosphate or TSP [Ca(H2PO4)2] was developed in the USA to produce  a more concentrated source of P than SSP. Production of super phosphoric acid (75-77%) paved the way for the production of concentrated superphosphate (54% P2O5) and ammonium polyphosphates such as 16-60-0 (15). In India, TSP was first produced in 1968 at Ambernath in Maharashtra but this production has ceased for the past 20 years.

Fertilisers Containing NP and NPK

Mono Ammonium Phosphate or MAP (NH4H2PO4) and Diammonium Phosphate or DAP (NH4)2HPO4 : Superphosphate was first ammoniated with aqua ammonia in the USA in 1926 to produce ammonium phosphate.Two grades of DAP were made commercially in the USA in 1920 and in 1954 the first large-scale continuous production of DAP based on wet process phosphoric acid began. Modern processes for the production of MAP and DAP were developed at the Tennessee Valley Authority TVA), USA .These fertilisers are mostly used as intermediates to produce other fertilizers but in India much of DAP is used for direct application to soils. In India, DAP production started in 1967 at Vadodara, Gujarat. DAP today is the dominant source of finished phosphate in India accounting for 63% of total P2O5 and also 9.4% of total N.

Nitro-Phosphates:

Also known as nitric phosphates or ammonium nitrate phosphates (ANPs), these are a group of fertilizers in which phosphate rock is acidulated with nitric acid unlike in super phosphates where sulphuric/phosphoric acid is used or ammonium phosphates where phosphoric acid is used to acidulate the rock. The nitro phosphate process was developed by Erling Johansen in Norway in 1927/28 who named it as the ODDA process after the town of ODDA where it was developed. Another process for the production of nitrophosphates is the PEC process which refers to the French firm Potasse et Engrais Chimiques. Nirophosphate was first commercially produced in Norway around 1938. At present, several types of modifications are available resulting in the production of a variety of grades. All nitro phosphates contain 50% of their N as nitrate and 50% as ammonium. The water soluble proportion of their total P2O5 varies from 30% to 90% depending on the process used. In India, the production of nitrophosphates started in 1965 at Trombay, Mumbai. At that time, one grade contained 30% water soluble P2O5 and the other grade contained 50-60% water soluble P2O5. Production of nitrophosphate containing 85% water soluble P2O5 started in India in1991.   

Ammonium Phosphate Sulphate (APS):

Production of APS started as back as 1933. In India, these NPS complexes were first prepared at Udyogmandal in Kerala in 1960.The dominant grade produced today contains 20% N, 20% P2O5 and 13% S.

Urea Ammonium Phosphate UAP):

These are complexes of Mono ammonium phosphate + urea. Fertiliser based on ammonium phosphate and urea was produced in Japan, probably more than 50 years ago. Later, technology for the production of urea ammonium phosphate was also developed at the Tennessee Valley Authority (TVA) in the USA. This technology was first used on a commercial scale in India for the production of UAP 28-28-0 in 1968 at Vishakhapatnam, Andhra Pradesh.

NPK complex fertilizers:

Interest in the development and production of NPK complexes followed the development of ammonium phosphates and the easy availability of MOP, the potash source.In India, production of NPK complex started through the nitrophosphate route in 1965. Production of other complexes followed, for example complexes 12-32-16 and 10-26-26 in 1974 at Kandla, Gujarat; 19-19-19, 14-35-14 etc in 1975 at Zuarinagar, Goa; 17-17-17 in 1976 at Manali, Chennai. Since then, these and other similar NPK complex grades have been replicated by several manufacturers.

Slow Release/Controlled Release Fertilisers

Interest in conserving and controlling the rate of release of soluble fertilizer N led to the development of slow release fertilizers. Terms currently gaining currency for all such fertilizers are “Controlled Release Fertilizers”(CRF) and “Enhanced Efficiency Fertilisers”(EEF). The best known of the group and longest in use are the urea formaldehydes or “Ureaforms).The process for the production of ureaform was patented by BASF in Germany in 1924.These were patented for use as fertilizers in 1947 in the USA and were commercially produced in the USA in 1955 (9). Ureaforms are prepared by reacting urea with formaldelyde under controlled conditions keeping U:F mole  ratio >1. Typically, ureaform contains 38% N. The family of ureaforms contains a range of product depending on polymerization. Urea form consists largely of longer UF polymers, methylene ureas (MU) which evolved during the 1960s and onwards are intermediate chain length polymers while methylene diurea (MDU) which was developed in the 1980s consists of short chain polymers.
Later, a whole range of slow and controlled release fertilizers were developed. Out of these a mention may be made of isobutylidene diurea (IBDU) containing 31% N (90% water insoluble). IBDU-based formulations are being produced in Belgium, Germany and  Japan. Another CRF is crotonyledene diurea or CDU containing about 32% N. It is produced in Japan which also accounts for most of the consumption.

Among coated fertilizers, one of the best known and publicised fertilizers  is S-coated urea. Sulphur coated urea was first developed by the TVA of USA in the early 1960s for which it was granted a patent in 1967 (US Patent 3,295,950). Each prill of urea was given a coating of elemental S. Bench scale   production also started in 1961. It was first produced in a pilot plant and marketed in the UK as ”Gold-N” (5). First large scale plant for the production of SCU was set up in the mid 1970s in Canada followed by the first commercial production facility in the USA.  NPK fertilizers coated with sulphur have also been developed, in Japan as discussed by Miyata (12). SCU and several other S-cated fertilizers are estimated to account for about 45% of total coated fertilizer production.
 Another important class of CRFs which have evolved on the years are polymer coated fertilizers. These were initially produced in the USA starting in 1967 under the brand name “Osmocote”. Although several fertilisers can be coated with polymers, most of the products are polymer coated NPK (9) The development and characteristics of several slow and controlled release fertilizers has been dealt with in several publications (3,9,12,13,14,19).A recent detailed account of the development of CRFs has been provided by Landels (9).
In conclusion,  various innovative, challenging and dedicated developments by intelligent and hard working chemists, technologists and entrepreneurs gave birth to and shaped in the fertilizer sector, The people, the places and the products which shaped the history of fertilisers are few in number. The major places of action were Germany, Norway, UK and the USA. The major contributions were those of Liebig, Murray, Lawes, Haber, Bosch, Frasch, The TVA Group and those who discovered major mineral deposits. The commercial fertilizers which stand out and account for bulk of the tonnage are also just a few. These are Urea, DAP, SSP, MOP and NP/NPK complexes. Leaders are always few in number whether one talks of men or materials.


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