Fertilizer ammonium sulfate used

Genders et al. (Eleetrosynthesis Co Inc.) in conjunction with the Ormiston Mining Company [264-266,282a] have developed a new technology which converts sodium sulfate into two useful products ammonium sulfate (used extensively as a fertilizer) and sodium hydroxide, The scheme of the modified cell is shown in Fig. 34. 

Chilean saltpeter, NaNOs. was the first of the chemical nitrogenous fertilizers. Ammonium sulfate. (NRshSO-t. made available as a byproduct of coal-gas produced in large quantities prior to wide use of natural gas. 

Sulfur is present in ammonium sulfate, used as a fertilizer, bul ammonium sulfate is only one of many fertilizers that may he used. Elemenlal sulfur and sulfur-containing compounds are also used tor controlling various plant pests. The soils also pick up sulfur trout air pollution Nevertheless, soil analysis should be made to provide an aceurale diagnosis of whether or not a particular soil may require additional sulfur. 

As an inexpensive source of acid, a large amount of the sulfuric acid that is produced is used for the manufacture of other mineral acids. It is also used to produce sulfates, such as ammonium sulfate (a low-grade fertilizer), sodium sulfate (used in the production of paper), and aluminum sulfate (used in water treatment), as well as organic sulfates (used as surfactants). Sulfuric acid is also a good catalyst for many reactions, including the transformation of ethanol into ethylene or ethyl ether. 

The above-discussed acid retardation and base retardation in the immobiUzed Uquid phase could be compared with the so-called salting-out effects. However, this term is hardly applicable to the case of salt retardation, the first example of which was demonstrated by a successful removal of small amounts of NH4CI from a concentrated brine of (NH4)2S04. This practically important problem arises in the manufacture of caprolactam, where large amounts of sulfuric acid are converted into ammonium sulfate used for the preparation of the crystalline fertilizer. The new process of ISE on nanoporous NN-381 resin allowed an effective purification of very large volumes of concentrated sulfate brine, due to the fact that small ions of NH and Cl are efficiently squeezed into and retained in the finest pores of the sorbent [172]. We consider this salt retardation process as a convincing proof of our interpretation of the mechanisms of the new electrolyte separation process. 

The same process, of course, led to the production of chemical fertilizers, ammonium sulfate, ammonium nitrate, and urea, which benefited mankind. The green revolution (an efficient production of rice) was possible only with a massive use of chemical fertilizers. Now this has resulted in the deterioration of soils, and a further increase by this technology alone in agricultural productivity may not be very likely. This story teUs us that use of technology has always both positive and negative aspects. We need to be very judicious in applying science to technology. 

Mixed with additives, urea is used in soHd fertilizers of various formulations, eg, urea—ammonium phosphate (UAP), urea—ammonium sulfate (UAS), and urea—phosphate (urea + phosphoric acid). Concentrated solutions of urea and ammonium nitrate (UAN) solutions (80—85 wt%) have a high nitrogen content but low crystallization point, suitable for easy transportation, pipeline distribution, and direct spray appHcation. 

When coal is coked at a temperature of approximately 1000°C, about 70—75% of the product is coke. Nearly 20% of the product is a light gas, mostiy methane and hydrogen, that typically is used as fuel to heat the ovens. Coal tars amount to about 4% of the product and light oil or naphtha is about 1%. Ammonia is recovered in an amount equal to about 0.3% of the feed coal. The ammonia is usually converted to ammonium sulfate and sold as a fertilizer. Littie or no ammonia [7664-41-7] is produced inlow temperature carbonization (3). 

Ammonium Sulfate. Historically ammonium sulfate was important as a fertilizer. However, since the introduction of ammonium nitrate and urea, the relative importance of ammonium sulfate worldwide has steadily decreased. In the year ended June 30, 1990, ammonium sulfate furnished only about 4% of the fertilizer nitrogen used in the United States (Fig. 3) and worldwide (Fig. 6). 

Essentially all the ammonium sulfate fertilizer used in the United States is by-product material. By-product from the acid scmbbing of coke oven gas is one source. A larger source is as by-product ammonium sulfate solution from the production of caprolactam (qv) and acrylonitrile, (qv) which are synthetic fiber intermediates. A third but lesser source is from the ammoniation of spent sulfuric acid from other processes. In the recovery of by-product crystals from each of these sources, the crystallization usually is carried out in steam-heated sa turator—crystallizers. Characteristically, crystallizer product is of a particle size about 90% finer than 16 mesh (ca 1 mm dia), which is too small for satisfactory dry blending with granular fertilizer materials. Crystals of this size are suitable, however, as a feed material to mixed fertilizer granulation plants, and this is the main fertilizer outlet for by-product ammonium sulfate. 

Fig. 18. TVA-type cogranulation process with preneutralizer, as used for production of granular mixed fertilizers. Feed materials such as ammonium sulfate, ammonium nitrate, urea, superphosphates, sulfuric acid, and potash are used.

Iron. As with copper, some dozen or more materials are used as fertilizer Hon sources. These include ferrous and ferric oxides and sulfides and ferrous ammonium phosphate [10101 -60-7] ferrous ammonium sulfate [10045-89-3] frits, and chelates. In many instances, organic chelates are more effective than inorganic materials. Recommended appHcation rates range widely according to both type of micronutrient used and crop. Quantities of Fe range from as low as 0.5 kg/hm as chelates for vegetables to as much as a few hundred kg/hm as ferrous sulfate for some grains. 

An additional mole of ammonium sulfate per mole of final lactam is generated duting the manufacture of hydroxylamine sulfate [10039-54-0] via the Raschig process, which converts ammonia, air, water, carbon dioxide, and sulfur dioxide to the hydroxylamine salt. Thus, a minimum of two moles of ammonium sulfate is produced per mole of lactam, but commercial processes can approach twice that amount. The DSM/Stamicarbon HPO process, which uses hydroxylamine phosphate [19098-16-9] ia a recycled phosphate buffer, can reduce the amount to less than two moles per mole of lactam. Ammonium sulfate is sold as a fertilizer. However, because H2SO4 is released and acidifies the soil as the salt decomposes, it is alow grade fertilizer, and contributes only marginally to the economics of the process (145,146) (see Caprolactam). 

Manufacture. Historically, ammonium nitrate was manufactured by a double decomposition method using sodium nitrate and either ammonium sulfate or ammonium chloride. Modem commercial processes, however, rely almost exclusively on the neutralization of nitric acid (qv), produced from ammonia through catalyzed oxidation, with ammonia. Manufacturers commonly use onsite ammonia although some ammonium nitrate is made from purchased ammonia. SoHd product used as fertilizer has been the predominant form produced. However, sale of ammonium nitrate as a component in urea—ammonium nitrate Hquid fertilizer has grown to where about half the ammonium nitrate produced is actually marketed as a solution. 

Economic Aspects and Uses. Almost all ammonium sulfate is used as a fertilizer for this purpose it is valued both for its nitrogen content and for its readily available sulfur content. In 1986/1987 United States consumption of ammonium sulfate was 0.57 million metric tons (34) world consumption during the same period was estimated at 13.3 million metric tons. In North America ammonium sulfate is largely recovered from caprolactam production. 

Ammonium sulfate is a good fertilizer for rice, citms, and vines, and can be especially useful for some sulfur-deficient or high pH soils. Nonfertilizer uses include food processing, fire control, tanning, and catde feed. 

Sulfuric acid is the most important sulfur-containing intermediate product. More than 85% of the sulfur consumed in the world is either converted to sulfuric acid or produced direcdy as such (see Sulfuric acid and sulfur trioxide). Worldwide, well over half of the sulfuric acid is used in the manufacture of phosphatic fertilizers and ammonium sulfate for fertilizers. The sulfur source may be voluntary elemental, such as from the Frasch process recovered elemental from natural gas or petroleum or sulfur dioxide from smelter operations. 

The anaerobic reaction of sulfur dioxide with aqueous ammonia produces a solution of ammonium sulfite [10192-30-0]. This reaction proceeds efficientiy, even with a gas stream containing as Httie as 1 wt % sulfur dioxide. The sulfur dioxide can be regenerated at a high concentration by acidulation or by stream stripping of the ammonium sulfite solution, or the sulfite can be made to precipitate and the ammonia recovered by addition of lime (243). The process can also be modified to produce ammonium sulfate for use as fertili2er (244) (see Fertilizers). In a variant of this process, the use of electron-beam radiation cataly2es the oxidation of sulfur dioxide in the presence of ammonia to form ammonium sulfate (245). 

Sulfur (qv) is among the most widely used chemicals and often considered to be one of the four basic raw materials of the chemical iadustry. In 1993, worldwide production of sulfur reached 55 million metric tons (1). Production of sulfuric acid consumes the vast majority (- 90%) of sulfur (2) (see Sulfuric acid and sulfur trioxide). This acid is a steppiag stone ia the production of other sulfur-containing compounds, most notably ammonium sulfate fertilizer which accounts for 60% of the total worldwide sulfur consumption (2) (see Ammonium compounds Fertilizers). 

This subsection discusses the production of ammonia, urea, ammonium sulfate, ammonium nitrate (AN), calcium ammonium nitrate (CAN), and ammonium sulfate nitrate (ASN). The manufacture of nitric acid used to produce nitrogenous fertilizers typically occurs on site and is therefore included here. 

The emergent SO2 is then fed into a contact process for H2SO4 (p. 708). Alternatively, ammonia and CO2 can be passed into a gypsum slurry to give ammonium sulfate for use in fertilizers ... 

Sulfuric acid is the most heavily produced inorganic chemical worldwide, the annual production in the United States alone being more than 4 X 1(J10 kg. The low cost of sulfuric acid leads to its widespread use in industry, particularly for the production of fertilizers, petrochemicals, dyestuffs, and detergents. About two-thirds is used in the manufacture of phosphate and ammonium sulfate fertilizers (see Section 15.4). 

C03-0103. Four commonly used fertilizers are NH4 NO3 (ammonium nitrate), (NH4)2 SO4 (ammonium sulfate), (NH2)2 (urea), and (NH4)2 HPO4 (ammonium hydrogen phosphate). How many kilograms of each of these would be required to provide 1.00 kg of nitrogen ... 

The production of nitrogen fertilizers is a major activity of the chemical industry. Every year, the top 15 chemicals in industrial production in the United States include several nitrogen-containing compounds whose major use is in fertilizers. Molecular nitrogen serves as the primary source of nitrogen for chemical production. Gaseous ammonia (NH3), which is synthesized from N2 and H2, can be injected directly into the ground, where it dissolves in moisture in the soil and serves as a fertilizer. Ammonia is more widely used in reactions with acids to produce other fertilizers Ammonia and nitric acid produce ammonium nitrate (NIL) NO3), while ammonia and sulfuric acid produce ammonium sulfate. These chemicals and urea,... 

Hydroxylamine (hyam) is used in the production of caprolactam, a key raw material for the manufacture of Nylon-6. Several technologies exist for the production of caprolactam with a key difference being the amount of byproduct ammonium sulfate, a low cost fertilizer, formed. The hyam used in the process is produced by... 

An enormous quantity of ammonium nitrate is produced annually primarily for use a fertilizer and also as an explosive. Ammonium sulfate, ammonium phosphate, and urea are also used as nitrogen-containing fertilizers. They are produced by the reactions... 

Uhde-Hibemia A process for making a mixed ammonium nitrate - ammonium sulfate fertilizer (ASN) - which is less liable to explode than ammonium nitrate. Sulfuric acid is added to aqueous ammonium nitrate and ammonia gas passed in. The double salt crystallizes out. Additives are used to improve the handling characteristics of the product. Developed by Hibernia and licensed to Friedrich Uhde. See also Victor. 

---