Search Documents

By Paul Queneau

Some years from now, perusal of the unfolding saga of the nickel family will show that the year 1968 was the herald of change-both in the geography of its endeavors and in its technology. No one should doubt any longer that oxide ores of nickel have come of lusty age-their heavyweight stature in the Caribbean area and in the Western Pacific can be shrunk only by immersion in the politics of unhappiness. The sulfide branch of the family has been augmented afar off by substantial ore deposits in western Australia-right across the globe from Sudbury-and in southern Africa, 9000 miles from the nickel hub. The Foreword of the 1961 AIME volume, dealing with the extractive metallurgy of copper and nickel, noted that "the dead hands of nitrogen" had been lifted from oxidation reactions utilizing air and that the industry was on the threshold of under- standing this fact. Here, at least, nonferrous industry had led its ferrous counterpart in the commercial use of tonnage oxygen in liquid phase pyrometallurgy-the reference is to oxygen flash smelting. Today large oxygen-producing plants are blossoming everywhere and the fruits which will follow are many and varied. Among them is Inco's forthcoming use of the top-blown oxygen converter for sulfide melts. The bell tolls for those "pyro- metallurgical dinosaurs" which still stalk smelter aisles the world around. Silicate oxide nickel ores will rejoice in the glow of modern elevated temperature chemical metallurgy in its various manifestations, vindicating the bulldog spirit of that ancient of clans, the hot metal men-including the renovator of Le Nickel's Doniambo Works.

Jan 10, 1968

By Gen-ichi Nakazawa, Masamichi Fujimori, Ichiro Doi

INTRODUCTION The major products of nickel industry in Japan are the electrolytic nickel (E-Ni), the ferro-nickel (Fe-Ni) and the nickel oxide sinter (NOS), totaling in production to 90 - 100 X 103 tons/year in terms of pure nickel content, and sharing approximately 20% for E-Ni, 10% or less for NOS, and the rest for Fe-Ni. The raw materials to be used for these products depend totally upon the imports from abroad; matte, the raw material used in the production of E-Ni, is from Australia and Indonesia; matte for the NOS is from Indonesia and New Caledonia; and garnierite, the raw material for Fe-Ni, is imported in bulk from New Caledonia, Indonesia and the Philippines. This report describes the acquisition of these raw materials, the production processes, trend of supply-demand, problem areas and the measures taken, and so forth, in connection with the nickel industry in Japan. ELECTROLYTIC NICKEL 1. History The nickel industry in Japan began in 1939 by the Sumitomo Metal Mining Co., Ltd. (SMM) with 150 tons E-Ni/month under the blast furnace smelting and the metal anode electrolysis. This was temporarily suspended after the end of last World War II, but resumed in 1952 with garnierite of New Caledonia as a raw material. Since then, the production capacity has been expanded incidentally to the increase of demand. However, since the smelting of garnierite contained about 2% nickel was very costly, the smelting process had been changed to smelt the briquettes of the mixture of garnierite and nickel sulfide concentrate imported from Canada and Australia. In 1975, this smelter was closed, and SMM's nickel refinery used matte from Western Mining Corp. (WMC) of Australia as a raw material. The refining process had been the metal anode one. The crude nickel oxide derived from roasting the high grade nickel matte had been melted and reduced with coke in the electric furnace and cast into anode. In 1970, a new refinery was constructed to produce 1,000 tons Ni/month under the matte anode process, and further, in 1976, the old refinery was converted into the matte anode process, thus resulting in the total production capacity of 1,690 tons Ni/ month today under the matte anode process. Shimura Kako Co., Ltd. began in 1951 to produce a little of E-Ni, and in 1955, they constructed a shaft furnace smelter with New Caledonian garnierite as a raw material to begin the E-Ni production under the matte anode process. Its monthly production reached 400 tons in 1957, but it discontinued its smeltering in 1963 to convert to the matte import from S. Le Nickel, WMC and INCO. In 1979, it changed the source of matte supply from the above to Soroako of Indonesia, discontinued the E-Ni production in 1979, and arranged for a total toll contract with Sumitomo. Meanwhile, SMM has developed a very distingished process for nickel-cobalt separation and refining by a solvent extraction method from nickel and cobalt mixed sulfide generated as a by-product in the nickel recovering process from laterite under the Nicaro process. Nippon Mining Co., Ltd. (NMC) also developed its own process. The plants under these processes were constructed in 1975, with the monthly production capacity of 230 tons of nickel and 130 tons of cobalt by SMM, and 300 tons of nickel and 110 tons of cobalt by NMC. SMM imports the raw material from the Marinduque Mining and Industrial Corp. of the Philippines, while NMC from Queensland Nickel Pty. Ltd. of Australia. 2. Production Status 2.1 Producers and materials Today, SMM holds the monthly E-Ni production capacity of 1,920 tons, of which 1,690 tons are from the matte anode process, and the remaining 230 tons are from the mixed sulfide as a raw material. NMC also uses the mixed sulfide as a raw material for a production of 300 tons/month. [ ] Most of SMM's raw material, nickel matte, is imported from WMC of Australia, partly using the Soroako matte from Indonesia. An example of material analysis is given in Table 1. Matte is a raw material for E-Ni and NOS, and the major sources of matte supply at present are Australian WMC and Indonesian Soroako, occupying ap-

Jan 1, 1982

By R. G. Whittemore, R. Derry

Nickel metal, in powder form, has been produced by pressure reduction, with hydrogen gas, of slurries of nickel hydroxide at temperatures up to 250°C. The nickel hydroxide was obtained by precipitation from nickel chloride and nickel sulphate solutions, using both magnesium oxide and calcium oxide. Rates of reduction and yields were determined as a function of temperature, hydrogen overpressure, seed addition, and the amount of alkali used. The mechanism of reduction of slurries obtained from the sulphate system was studied, and major differences between the sulphate system and the previously examined chloride system investigated. Specifically, in the sulphate system, contra the chloride system, no seeding was necessary, plating and densification were virtually absent and only short induction periods occurred. Grades of product are given and the use of this process in the recovery of nickel from laterites is discussed. The selective reduction of nickel from mixed hydroxide slurries and effluent treatment plant sludge has also been examined.

Jan 1, 1973

By E. S. Moore

ALTHOUGH nickel was in use in alloys long before the Christian era, the metal was not discovered until 1751, when Cronstedt recognized it in niccolite from Sweden. The Chinese apparently used a nickel alloy, known as "pahfong" thousands of years ago and Persian coins dating farther back than 200 B.C. consist of a copper-nickel alloy similar to some of those now in use in coins. The pure metal was first prepared about 1775 and the metal was refined for commercial purposes some years later. The nickel industry did not attain much prominence until the ores in New Caledonia were discovered. Exports of ore from that country began in 1875 and since that date there has been an ever-increasing world output of nickel and a great expansion in the uses of the metal except during short periods of commercial and industrial depression. Previous to 1875, for a number of years, Norway was the chief producer, although the metal was mined also in Sweden, Finland, Italy, Germany, Austria, France, China, the United States and other countries. With the dis-covery of nickel deposits in the Sudbury district, Ontario, a new factor was introduced into the nickel industry and Sudbury has since become the overwhelmingly dominant feature in the world's nickel markets. Although nickel was first discovered in Canada as early as 1848 near the north shore of Lake Huron and nickel-copper sulfides were found in 1856 by surveyors working close to the present location of the important mine at Creighton, in the Sudbury field, it was not until 188.3 that any importance was attached to this field. In that year copper sulfide attracted attention where the main line of the Canadian Pacific railroad was being projected across Canada to the Pacific coast. Mining began near this discovery in 1889 but in the meantime operations had begun in 1886 in other parts of the field and by 1890 about 100,000 tons of ore had been raised. In the Sudbury field, as in Norway and at the old Lancaster Gap mine in Pennsylvania, the ore was first mined for its copper content and difficulty in the refining of the copper led to the discovery of the important proportions of nickel in the ore. No. 3 property of the Inter-national Nickel Co., now known as the Frood, the greatest deposit in the

Jan 1, 1932

By John T. Eash

DURING the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin, 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. SELECTION OF COMPOSITION While the final criterion of the suitability of an alloy for a bearing must 0f course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstructure, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig. I. In addition, the tin bronze contains the hard alpha + delta eutectoid constituent distributed through-

Jan 1, 1945

By Byron B. Morton

NICKEL-BEARING alloys are associated with petroleum in the fields of exploration, production, and refining. In the first- named field the geologist of today makes use of such instruments as the seismograph, torsion balance, and magnetometer, the selection of proper alloys and metals for the manufacture of which is an important matter. Nickel-bearing alloys are useful for parts that require resistance to corrosion or that must have non-magnetic properties. Where special co- efficient of thermal expansion are de- sired, they are obtained by using alloys high in nickel (20 to 60 per cent), since, by varying the nickel contents, alloys can be obtained ranging fro111 "Invar", with a low expansion between -40 and 175 cleg. F., to those with coefficients of expansion exceeding that of steels. The latter are obtained by additions of chromiurn to the alloys. Alloys containing 50 to 80 per cent of nickel, which possess high magnetic permeability, find application in certain instruments where this property is important.

Jan 1, 1935

By Leon Hart

THE nickel-chromium alloys of importance are those containing iron and those free from iron. The most important alloys containing iron, with regard to high tonnage, are the nickel-chromium steels. Straight nickel steel was introduced about the year 1889, but it was not until 1895, when it was found that the addition of chromium greatly increased the FIG. 1.-RESISTIVITY OF NICKEL-CHROMIUM-IRON ALLOYS. strength and resistance to shock, that nickel-chromium steels came into use. The three types of nickel-chromium steels developed at this time were: Type 1, containing 3.50 per -cent. nickel and 1.50 per cent. chromium; type 2, containing 2.00 per cent. nickel and 1.00 per cent. chromium; and type 3, containing 1.50 per cent. nickel and 0.50 per cent. chromium.

Jan 1, 1921

By Laurence Delisle, Aaron Finger

THE alloys formed by the addition of nickel to iron by convelltional metallurgical procedures show physical properties that differ widely from those of the individual metals. The effect of alloying on the mechanical properties is most pronounced in alloys containing between 15 and 25 per cent nickel. The tensile strength of an alloy containing, for example, 20 per cent nickel and 80 per cent iron (with 0.06 per cent carbon), in an annealed condition, is above 150,000 lb. per sq. in.? owing to a martensitic type of transformation, as compared with about 50,000 lb. per sq. in. for pure iron in the same condition. The object of this work was to determine whether the same beneficial alloying effect could be obtained in alloys of iron and nickel prepared by powder metallurgy technique. PROCEDURE Bars and pellets for tension and compression tests, respectively, were made. Two groups of specimens were prepared: (I) by cold-pressing the powders and sintering; (2) by cold-pressing the powders, sintering, repressing and resintering. Raw Materials Nickel powder supplied by Metals Disintegrating co., marked MD-151, was used. A typical analysis of this powder was as follows: sulphur, 0.040 per cent; copper, 0.18; iron, 0.23; manganese, 0.002; magnesium, 0.001 5 ; lead, 0.035; tin, 0.025 ; silicon, 0.08; chromium, 0.008. Electrolytic iron powder supplied by Plastic Metals Inc. was used. A representative chemical analysis for impurities other than gases, supplied by the vendor, gave the following results: carbon, 0.005 per cent; manganese, 0.002; silicon, 0.003; phosphorus, 0.001; sulphur, 0.004; nickel, 0.008. The fractions from these powders passing a 3 2 5-mesh sieve were reduced in hydrogen at 600°C. for one hour, to clean the surfaces of the particles. The reduced powders, slightly caked, were ground in a mortar and screened again through a 325- mesh sieve. Mixing The proper proportions of the powders were mixed overnight on rolls, in glass jars fitted with iron-wire baffles to break aggregates of particles that might form. Pressing All specimens were compacted on hydraulic presses. The pellets were compacted in a cylindrical die, ½ in. diameter. The ratio of thickness to the diameter of the pellets was maintained as nearly as possible at 0.9, as specifed for standard short compression pieces. The tensile bars were made by compacting 30 grams of powder. Their shape is shown in Fig. I. The compacting pressures for the pellets and the tensile bars were:

Jan 1, 1946

By Walter V. Knopp, Laurence Delisle

INTRODUCTION THE aim of this work was the preparation of nickel-steels from elemental metal powders by powder metallurgy techniques. It was known that plain carbon steels could be made from a mixture of iron powder and graphite and that the effect of carbon on iron in powder form was of the same nature as that produced in fusion metallurgy. The problem in making nickel steels from elemental powders consisted therefore in finding out whether sufficient diffusion of the nickel and other incidental metals normally present in such steels could be induced in the solid state to modify the properties of plain carbon steels made from powders and produce the beneficial effect of alloying. The composition selected originally was that of an S.A.E. 2330 steel. Metal powders, in the proportion corresponding to that composition, were mixed with graphite, pressed, and heated at different temperatures for different periods of time, to produce bonding of the metal particles and mutual diffusion of the various elements without melting. Temperatures up to 1325°C and sintering periods as long as 6 hr were first investigated because it was expected that such conditions would produce maximum diffusion with an accompanying improvement in the properties of the alloy. It was found that, although diffusion proceeded to a large extent under the conditions investigated, it would not be complete unless sintering were carried out at a high temperature for much longer than 6 hr. Relatively high temperatures and long sintering times are objectionable from a practical point of view, particularly when a low cost material is to be produced, because they necessitate the use of special, costly equipment. Work could be done to improve the diffusion of iron and nickel by changing conditions other than the sintering temperature and time, i.e., finer primary or alloy powders could be used. However, a marked change in the properties of the steel had been observed even with only partial diffusion. It was thought, therefore, that instead of trying to improve the diffusion, advantage might be taken of its incompleteness to produce a special structure consisting, in the unquenched condition, of a hard constituent, rich in nickel, dispersed in a tough pearlitic matrix. Steels with such a structure, not readily obtainable by fusion, should have desirable mechanical properties. Besides, it should be possible to prepare them from elemental powders under economical conditions. This latter alternative was therefore adopted for the second phase of this work. This report is divided into four parts: 1. General Procedure. 2. Effect of Sintering Temperature. 3. Effect of Varying the Nickel Content. 4. Effect of Alloying Elements. GENERAL PROCEDURE The general technique of cold pressing as used in powder metallurgy was applied.

Jan 1, 1948

Mineral Industries education as an entity, again and again has sought recognition, always to be turned aside or ignored.1 The incident mentioned in Lost Chapter was only the first of a series of disappointments. The Land-Grant Act is camouflaged here and there in the name of progressive education. A new interpretation may be in the best interests of society in so far as the goose is not killed that lays the golden egg. The primary objective of the act is still "agriculture and mechanic arts" but mechanic arts is not alone mechanical arts or engineering. Mechanic arts was used in a broad sense as a symbol of creative effort in locating and winning the fundamentals of existence - plants, animals, and minerals - from Mother Earth, their primary processing and treatment into foodstuffs and raw materials of industry, their manufacture into useful articles of commerce, and, last, their distribution and utilization. Significantly the great agricultural industry is now at least half mechanic arts. The Association of Land-Grant Colleges and Universities has neglected the mineral kingdom shamefully. The Association embraces Divisions of Agriculture, Arts and Sciences, Engineering, Home Economics, and Veterinary Medicine but has no division relating to the mineral industries.

Jan 1, 1950

By AIME AIME

N OW THAT the war is over it is possible to release data and correct some erroneous statements and impressions relative to the use of manganese-steel armor and helmets, which heretofore have been carefully guarded. The material of the helmets furnished to the English, American, and Belgian armies was invented by Sir Robert Hadfield, Bart., F.R.S., and was described in a paper read by him at the International Engineering Congress in August, 1893. The French helmet was 2 oz. lighter than the English but had a greatly inferior resistance. Tests showed that it was perforable at as low a velocity as 350 ft.- sec. impact of the standard shrapnel bullets. Helmets made of the Hadfield "Era" manganese steel kept out standard shrapnel bullets of the same quality at no less than from 750 to 950 ft.-sec. impact velocity. The respective energies were, in the case of the French helmet, only 0.021 ft.-tons, 46 ft.-lb., and in the British 0.095 ft.-tons, 213 ft.-lb. The German helmet was made of nickel-chromium steel and, although 12 oz. heavier and 12 per cent. thicker than the Hadfield, was not only perforate

Jan 1, 1920

By William E. Ford, Edward Salisbury Dana

The Niobates (Columbates) and Tantalates are chiefly salts of metaniobic and metatantalic acid, RNb2O6 and RTa2O6; also in part Pyroniobates, R2Nb2O7, etc. Titanium is prominent in a number of the species, which are hence intermediate between the niobates and titanates. Niobium and tanta¬lum also enter into the composition of a few rare silicates, as wöhlerite, låvenite, etc. The following groups may be mentioned: The isometric PYROCHLORE GROUP, including pyrochlore, microlite, etc. The tetragonal FERGUSONITE Group, including fergusonite and sipylite. The orthorhombic COLUMBITE Group, including columbite and tantalite. Also the orthorhombic SAMARSKITE GROUP, including yttrotantalite, samarskite, and ånnerodite. The species belonging in this class are for the most part rare, and are hence but briefly described.

Jan 1, 1922

By William E. Ford, Edward Salisbury Dana

The Nitrates being largely soluble in water play but an unimportant r81e i~ Mineralogy. SODA NITER. Rhombohedral. Axis c = 0.8276; rr" 1071 A 7101 = 73' 30'. Homeo- morphous with calcite. Usually massive form, as an incrustation or in beds. Cleavage: r (1011) perfect. Fracture conchoidal, seldom observable. Rather sectile. H. = 1.5-2. G. = 2'262.29. Luster vitreous. Color white; also reddish brown, gray and lemon-yellow. Transparent. Taste cooling. Optically -. w = 1'5874, e = 1'3361. Camp. - Sodium nitrate, NaN03 = Nitrogen pentoxide 63'5, soda 36'5 = 100.

Jan 1, 1922

By Horace R. Graham

CHEMICAL nitrogen and the "nitrates" of commercial significance are derived mainly from three basic sources: (1) the natural deposits in the form of nitrate-bearing earth and clay, which, being largely water-soluble, can exist only in the most arid portions of the earth; (2) coal, which yields not only nitrogen but also the additional by-product hydrogen required for the synthesis of ammonia and its compounds; (3) the atmospheric air, which contains 75.5 pct by weight of pure nitrogen gas. NATURAL NITRATE DEPOSITS Occurrence Although natural nitrate deposits consisting principally of the salts of sodium and potassium have been reported in Egypt, South Africa, Mexico, Argentina, Colombia, Peru and the USA, the only known natural nitrate resources of commercial importance are the vast deposits found in the Atacama, Tarapaca and Antofagasta regions of northern Chile, lying in a narrow strip 10 to 50 miles wide and roughly 450 miles long, between latitudes [19O] and [26OS]. In addition to yielding nitrates of sodium and potassium, these deposits are the source of the major portion of the world's supply of iodine. The nitrate-bearing ores known in Chile as caliche are variable in composition and may contain from 5 to 30 pct each of nitrate, chloride and sulphate. While the deposits are present chiefly in the form of the sodium salt, potassium, magnesium and calcium also occur in percent- ages from 0.1 to 5; usually as double salts with sulphate, which are but slightly soluble in nitrate leach solutions. These double salts are bloedite(Na2S04.MgS04.4H,0), glauberite (Na2S04.CaS04), polyhalite (K2SO4.- MgS04.2CaS04.2H20). Some deposits contain up to30 pct of their ni-

Jan 1, 1949

By O. Bergmann, R. E. Lueders, R. R. Ellefson, H. M. Brennecke, D. S. Davies

A new hydrometallurgical process has been developed to recover copper from sulfide ores. Copper is leached in a staged reactor system utilizing nitric and sulfuric acids at 105OC. Iron is removed from the pregnant liquor as a jarosite, and cathode copper is electrowon directly from the purified pregnant liquor. The spent electrolyte is recycled. Nitrogen oxides evolved from the leach are reconverted to nitric acid and are also recycled. Sulfur is rejected as So, jarosite, and gypsum. The process is highly versatile and can recover precious metals, molybdenum, and zinc when these elements are present. Continuous, integrated, semi-pilot plant operations using chalcopyrite ores demonstrated 99% copper leaching and production of cathode grade copper. Economic evaluation shows that the process is competitive with pyrometallurgical and other hydrometallurgical processes.

Jan 1, 1982

By T. J. Hudson, P. B. Queneau, J. D. Prater

The process parameters for effective utilization of nitric acid as an oxidant for copper-iron sulfides have been developed. Leaching variables found to be important were acid concentration, temperature, time, atmosphere, pressure, mineral type, particle size, and percent solids. Particular attention was devoted to analysis and control of fumes evolving during the oxidation. Data were recorded on metal extraction, elemental sulfur formation and oxidation, product gas composition and evolution rate, reagent consumption, and residue flotation response. The study was concluded by laboratory testing a flowsheet based on the foregoing observations. Ninety-eight percent of the copper contained in a chalcopyrite-bornite concentrate was recovered, requiring 1.6 lb of nitric acid to be regenerated externally per pound of copper extracted. Iron remained in the leach residue as hydrogen jarosite and was ultimately rejected from the system by froth flotation. Sixty percent of the sulfur contained in the copper concentrate reported in the elemental form; the remainder was oxidized to sulfate and eliminated with the hydrogen jarosite in the flotation tails or by neutralization of the solvent extraction raffinate with lime. Nitrogen was evolved primarily as NO and NOD; up to 3% N2O also was present. Gases containing sulfur were absent except when pyrrhotite was solubilized in the absence of soluble copper. In this case, HAS was evolved.

Jan 1, 1974

By R. A. Spitz, T. C. Frankiewicz, R. E. Lueders, D. S. Davies

Further development of the Nitric-Sulfuric Leach (NSL) process has led to an improved design of the leach and nitric acid recovery steps. NO produced in the leach step is reacted with oxygen, regenerating NO2, which is sparged directly into the leach reactor. Leaching is simplified to two steps, and the nitric acid plant is replaced with an oxidation recycle gas system. Laboratory work substantiated the concept and led to selection of operating conditions. The lab work also pointed to improved process control compared to use of nitric acid as the sole oxidant. Recovery of copper from purified pregnant liquor is modified to use air agitation electrowinning improving cathode quality and lowering tankhouse costs. Economic evaluation shows reduction of capital requirements from $2640 per annual ton to $2220 per annual ton in 1978 dollars for 45 kt/a of copper production.

Jan 1, 1982

By Ted C. Briggs

Nitrogen exists in two broad categories commonly designated as elemental nitrogen and fixed nitrogen. Elemental nitrogen is found in nature as a diatomic molecule and constitutes about 78%, by volume, of the earth's atmosphere. Fixed nitrogen is a common term used for nitrogen that is chemically bound to other elements. Although elemental nitrogen is very abundant, nonleguminous plants cannot utilize nitrogen unless it is in the chemically combined form. The content of this chapter is confined to fixed nitrogen since the uses and properties of elemental nitrogen and the fixed nitrogen compounds are different. Bacteria associated with legumes are able to fix atmospheric nitrogen, but not to the extent or in the locations required by modem agriculture. The need to use fertilizers containing fixed nitrogen compounds to grow food crops has been recognized for hundreds of years, and from antiquity farmers have used organic wastes such as animal manures, vegetable wastes, sewage sludge, fish scraps, etc., containing these compounds for fertilizers. The organic materials have a low nitrogen content, however, and cannot support large-scale food production. Known commercial-size deposits of natural nitrates containing much higher nitrogen content exist only in Chile, and the possibility of the discovery of other significant deposits is remote. The Chilean deposits were the major source of nitrogenous fertilizers until about 1913, when the Haber-Bosch process for the production of synthetic ammonia was developed. In the Haber-Bosch process, nitrogen reacts with hydrogen, at high temperatures and pressures and in the presence of a catalyst, to form ammonia. At present Chile is the only country in the world with a nitrate mining industry, and, although the mining of natural nitrates is an important industry in Chile, natural nitrates are relatively unimportant, worldwide, because of the adoption of fixed nitrogen processes. The relative amount of the world demand for fixed nitrogen that is derived from natural nitrates has declined in recent years and will continue to decline. Modern farmers are sophisticated in economic calculations such as cost to benefit ratios and, for the most part, they purchase plant nutrients which give the highest return on their investment. Natural nitrates cannot compete on a fixed-nitrogen cost basis with anhydrous ammonia and its derivative products. In a limited sense, the fixed nitrogen industry is mining the air. Modern plants use air, water, and, in most cases, natural gas to produce the ammonia that is now the key building block of the fixed nitrogen industry. To present an accurate picture of the industry, this chapter on nitrogen follows a format somewhat different from that of other chapters in this volume.

Jan 1, 1975

By R. D. Young, E. A. Harre

Nitrogen exists in two broad categories commonly designated as elemental nitrogen and fixed nitrogen. Elemental nitrogen is found in nature as a diatomic molecule and constitutes about 78%, by volume, of the earth's atmosphere. Fixed nitrogen is a common term used for nitrogen that is chemically bound to other elements. Although elemental nitrogen is very abundant, nonleguminous plants cannot utilize nitrogen unless it is in the chemically combined form. The content of this chapter is confined to fixed nitrogen since the uses and properties of elemental nitrogen and the fixed nitrogen compounds are different. Certain bacteria associated with legumes are able to fix atmospheric nitrogen, but not to the extent required by succeeding nonleguminous crops. The need to use fertilizers containing fixed nitrogen compounds to grow food crops has been recognized for hundreds of years, and from antiquity farmers have used organic wastes such as animal manures, vegetable wastes, sewage sludge, fish scraps, etc., containing these compounds for fertilizers. These organic materials have a low nitrogen content, however, and cannot support large-scale food production. Known commercial-size deposits of natural nitrates containing much higher nitrogen content exist only in Chile, and the possibility of the discovery of other significant deposits is remote. The Chilean deposits were the major source of nitrogenous fertilizers until the Haber-Bosch process for the production of synthetic ammonia was developed. In the Haber-Bosch process, nitrogen reacts with hydrogen at high temperatures and pressures and in the presence of a catalyst to form ammonia. Modern plants use air, water, and natural gas or other hydrogen sources to produce the ammonia that is now the key building block of the fixed nitrogen industry. Several major problems that developed in the 1970s continue with the nitrogen industry into the 1980s. These are (1) the continuing sharp escalation in the cost of feedstocks for ammonia production as well as all energy sources, and (2) the very steep increase in the investment cost of production facilities. More than 75% of the fixed nitrogen produced domestically is consumed as fertilizers. The types of materials used as fertilizers have changed significantly during the past years. There has been a trend from the use of low-analysis fertilizers to types which contain high percentages of plant nutrients. The average plant nutrient content (N + P2O5 + K2O) of fertilizers used in the United States has increased from 18% in 1930 to 32% in 1960 and today approaches an average of 44%. In the case of nitrogen fertilizers, the low analysis natural nitrates (16% N) gave way to ammonium sulfate (20% N) after about 1920. After World War II, ammonium nitrate (33.5% N) previously used in munitions, became established as the leading nitrogen fertilizer. Urea use as a fertilizer (46% N) began in the 1960s, and in the past 10 years has become the world's leading solid nitrogen fertilizer. Nitrogen Materials Anhydrous Ammonia-Anhydrous ammonia is a colorless gas at ambient temperatures and pressures and has a sharp pungent odor. Anhydrous ammonia is stored and transported as a liquid in high-pressure cylinders and tanks at ambient temperature, and in low-pressure tanks, barges, and ships at -28°F. Anhydrous ammonia is applied directly at 4 to 7-in. depths in the soil as a high-pressure liquid by special applicators, after which it expands to a gas that dissolves in the soil moisture or is absorbed on soil colloids. In other systems ammonia is metered into irrigation water and is thereby introduced into the soil.

Jan 1, 1983

By Herbert W. Huse

Nitrogen, and its compounds, unique among the materials described in this volume, is absolutely essential to the existence of the human race. Almost all minerals are important and the absence of any one of them would be sorely felt; but nitrogen is an integral part of the cycle of life itself. Man cannot live without nitrogen which, as an inert gas, composes the major part of the air he breathes; as compounds, nourishes the vegetation which he eats; and, as protein, forms a part of his very flesh and blood. Nature originally provided man with a vast reserve of usable nitrogen compounds in the form of fertile soil. She constantly replenishes the supply by "fixing" nitrogen in the air at the estimated rate of 400,000,000 tons per year (an insignificant 6 lb per acre) during electrical storms. She has also placed certain microorganisms in the soil which are able to "fix" nitrogen and convert it into forms which plants can use. Legumes like cow peas, soy beans, clover, and alfalfa have extraordinary roots which serve as stimulating hosts to these bacteria which, in turn, nourish the plant. By plowing in all or part of such crops, their above-average nitrogen content can be returned to the soil for other more useful crops. The mechanism for this recycle is supplied by "denitrifying" bacteria which attack the dead plant tissue and liberate nitrogen and ammonia. However, since one crop of grain, sugar beets, potatoes, tomatoes, etc., takes out a major portion of the nitrogen which a plowed-in legume crop can supply, this method of fertilization is obviously inadequate. Drastic intervention by man has become necessary to support the ever-growing population of the world.9,15,20 Old civilizations with a high population density, such as the Chinese, were able to exist for centuries by carefully tilling the soil, rotating crops, and returning to the soil all the nitrogen in vegetable wastes plus human and animal excreta. But the lack of a means for augmenting their supply of nitrogen placed a ceiling on further development and kept the mass of the population in a chronic state of undernourishment, frequently punctuated by famine. Nitrogen plays another important role in the life of mankind. In the form of explosives, nitrogen helps to wrest from the earth many materials needed for our material well-being. Also, in the form of explosives and propellants, nitrogen increased the destructiveness of wars to a point only exceeded by the fantastic power of atomic energy. Man's first really effective efforts to improve his position with respect to nitrogen began in the 18th Century with the mining of sodium nitrate. By the late 1880's this had become a big industry serving a large part of the world. In the late 1890's nitrogen, in the form of ammonia, was being recovered from coke-oven operations. In 1900 nitrogen, in the form of nitric oxide, was being obtained from the air by an electric-arc process. About 1904 another "fixation" process based on the reaction of nitrogen with calcium carbide to form cyanamide was commercialized. By 1913 the Haber-Bosch process of "fixing" atmospheric nitrogen by reacting it with hydrogen to produce synthetic ammonia was successfully applied on a large scale, first in Germany and then throughout the industrial areas of the world.9 All the above methods of obtaining nitrogen compounds are still in use and, between them, they assure mankind of adequate supplies for all time. While this fortunate situation is not unique amongst industrial raw materials, all too few of man's needs are so well in hand.

Jan 1, 1960