Ammonium sulfate, acidic

Figure 4.17. Polyphosphate content in nitrogen-starved cells of P. shermanii growing on lactate upon addition of ammonium sulfate. Acid-labile phosphate was assayed in alkaline-soluble fraction (a), salt-soluble fraction (b) and hot perchloric acid extract (c). Arrow indicates re-addition of ammonium sulfate. From Gaitan et al. (1982).

Ceric sulfate, O.IA Ce(lV) to Ce(lll). Dissolve 63.26 g of cerium(lV) ammonium sulfate dihydrate in 500 mL of 2N sulfuric acid. Dilute the solution to 1 L and standardize against the... 

Iron(II) ammonium sulfate hexahydrate, Q.IN Le(II) to Le(III). Dissolve 39.2139 g of LeS04 2(NH4)2S04 hHjO in 500 mL of IN sulfuric acid and dilute to 1 L. If desired, check against standard dichromate or permanganate solution. 

Foiin s mixture (for uric acid) dissolve 500 g of ammonium sulfate, 5 g of uranium acetate, and 6 mL of glacial acetic acid, in 650 mL of water. The volume is about a liter. 

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. 

The ratio of reactants had to be controlled very closely to suppress these impurities. Recovery of the acrylamide product from the acid process was the most expensive and difficult part of the process. Large scale production depended on two different methods. If soHd crystalline monomer was desired, the acrylamide sulfate was neutralized with ammonia to yield ammonium sulfate. The acrylamide crystallized on cooling, leaving ammonium sulfate, which had to be disposed of in some way. The second method of purification involved ion exclusion (68), which utilized a sulfonic acid ion-exchange resin and produced a dilute solution of acrylamide in water. A dilute sulfuric acid waste stream was again produced, and, in either case, the waste stream represented a... 

Important side reactions are the formation of ether and addition of alcohol to the acrylate to give 3-alkoxypropionates. In addition to high raw material costs, this route is unattractive because of large amounts of sulfuric acid—ammonium sulfate wastes. 

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.

Some of the principal forms in which sulfur is intentionally incorporated in fertilizers are as sulfates of calcium, ammonium, potassium, magnesium, and as elemental sulfur. Ammonium sulfate [7783-20-2] normal superphosphate, and sulfuric acid frequendy are incorporated in ammoniation granulation processes. Ammonium phosphate—sulfate is an excellent sulfur-containing fertilizer, and its production seems likely to grow. Some common grades of this product are 12—48—0—5S, 12—12S, and 8—32—8—6.5S. 

S. cerevisiae is produced by fed-batch processes in which molasses supplemented with sources of nitrogen and phosphoms, such as ammonia, ammonium sulfate, ammonium phosphate, and phosphoric acid, are fed incrementally to meet nutritional requirements of the yeast during growth. Large (150 to 300 m ) total volume aerated fermentors provided with internal coils for cooling water are employed in these processes (5). Substrates and nutrients ate sterilized in a heat exchanger and then fed to a cleaned—sanitized fermentor to minimize contamination problems. 

Coproductioa of ammonium sulfate is a disadvantage of the formamide route, and it has largely been supplanted by processes based on the direct hydrolysis of methyl formate. If the methanol is recycled to the carbonylation step the stoichiometry corresponds to the production of formic acid by hydration of carbon monoxide, a reaction which is too thermodynamicaHy unfavorable to be carried out directly on an iadustrial scale. 

Opa.nte. There are two methods used at various plants in Russia for loparite concentrate processing (12). The chlorination technique is carried out using gaseous chlorine at 800°C in the presence of carbon. The volatile chlorides are then separated from the calcium—sodium—rare-earth fused chloride, and the resultant cake dissolved in water. Alternatively, sulfuric acid digestion may be carried out using 85% sulfuric acid at 150—200°C in the presence of ammonium sulfate. The ensuing product is leached with water, while the double sulfates of the rare earths remain in the residue. The titanium, tantalum, and niobium sulfates transfer into the solution. The residue is converted to rare-earth carbonate, and then dissolved into nitric acid. 

Mitsubishi Gas Chemical Company Process. The commercial MMA manufacturing process based on sulfuric acid and acetone cyanohydrin suffers from the large quantities of ammonium sulfate produced. Because ammonium sulfate has only low value as fertili2er, regeneration of sulfuric acid from ammonium sulfate [7783-20-2] is required. Despite the drawbacks of using sulfuric acid, this technology is stiU the most widely practiced... 

The reaction is mn for several hours at temperatures typically below 100°C under a pressure of carbon monoxide to minimise formamide decomposition (73). Conversions of a-hydroxyisobutyramide are near 65% with selectivities to methyl a-hydroxyisobutyrate and formamide in excess of 99%. It is this step that is responsible for the elimination of the acid sludge stream characteristic of the conventional H2SO4—ACH processes. Because methyl formate, and not methanol, is used as the methylating agent, formamide is the co-product instead of ammonium sulfate. Formamide can be dehydrated to recover HCN for recycle to ACH generation. 

Qualitative Analysis. Nitric acid may be detected by the classical brown-ring test, the copper-turnings test, the reduction of nitrate to ammonia by active metal or alloy, or the nitrogen precipitation test. Nitrous acid or nitrites interfere with most of these tests, but such interference may be eliminated by acidifying with sulfuric acid, adding ammonium sulfate crystals, and evaporating to alow volume. 

Plants can also be pests that need to be controlled, particulady noxious weeds infesting food crops. Prior to 1900, inorganic compounds such as sulfuric acid, copper nitrate, sodium nitrate, ammonium sulfate, and potassium salts were used to selectively control mustards and other broadleaved weeds in cereal grains. By the early 1900s, Kainite and calcium cyanamid were also used in monocotyledenous crops, as well as iron sulfate, copper sulfate, and sodium arsenate. Prom 1915 to 1925, acid arsenical sprays, carbon bisulfate, sodium chlorate, and others were introduced for weed control use. Total or nonselective herbicides kill all vegetation, whereas selective compounds control weeds without adversely affecting the growth of the crop (see Herbicides). 

Petrochemicals are those chemicals produced from petroleum or natural gas and can be generally divided into three groups (/) aliphatics, such as butane and butene (2) cycloaliphatics, such as cyclohexane, cyclohexane derivatives, and aromatics (eg, ben2ene, toluene, xylene, and naphthalene) and (J) inorganics, such as sulfur, ammonia, ammonium sulfate, ammonium nitrate, and nitric acid. 

The neutralization of acids is of commercial importance. Three principal fertilizers, ammonium nitrate [6484-32-2], NH NO, ammonium sulfate [7782-20-2], (NH 2S04, and ammonium phosphate [10361-65-6], (NH PO, are made by reaction of the respective acids with ammonia. 

Ammonia is consumed in the manufacture of ammonium phosphates and ammonium sulfate by reaction with phosphoric acid and sulfuric acid, respectively. The phosphates may contain ortho- and polyphosphate values. Ammonium sulfate is also a by-product from other ammonia-using industries such as caprolactam (qv) and hydrogen cyanide (see Cyanides). 

Recovering ammonia as a by-product from other processes accounted for less than 1% of the total U.S. ammonia production in 1987. The principal source of by-product ammonia is from the coking of coal. In the coking operation, about 15—20% of the nitrogen present in the coal is Hberated as ammonia and is recovered from the coke oven gas as ammonium sulfate, ammonia Hquor, and ammonium phosphates. The recovery product depends on the scmbbing medium employed, sulfuric acid, milk of lime, and phosphoric acid, respectively. Ammonium sulfate recovery by the so-called semidirect process, is most widely employed. 

The gaseous ammonia is passed through electrostatic precipitators for particulate removal and mixed with the cooled gas stream. The combined stream flows to the ammonia absorber where the ammonia is recovered by reaction with a dilute solution of sulfuric acid to form ammonium sulfate. Ammonium sulfate precipitates as small crystals after the solution becomes saturated and is withdrawn as a slurry. The slurry is further processed in centrifuge faciHties for recovery. Crystal size can be increased by employing one of two processes (99), either low differential controUed crystallization or mechanical size enlargement by continuous compacting and granulation. 

The ammonium sulfate and sodium chloride are simultaneously dissolved, preferably ia a heel of ammonium chloride solution. The sodium chloride is typically ia excess of about 5%. The pasty mixture is kept hot and agitated vigorously. When the mixture is separated by vacuum filtration, the filter and all connections are heated to avoid cmst formation. The crystalline sodium sulfate is washed to remove essentially all of the ammonium chloride and the washings recycled to the process. The ammonium chloride filtrate is transferred to acid resistant crystallising pans, concentrated, and cooled to effect crystallisation. The crystalline NH Cl is washed with water to remove sulfate and dried to yield a product of high purity. No attempt is made to recover ammonium chloride remaining ia solution. The mother Hquor remaining after crystallisation is reused as a heel. 

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. 

Manufacture. Ammonium sulfate is produced from the direct neutralization of sulfuric acid with ammonia the heat of reaction is sufficient to evaporate all water if the concentration of the acid is 70% or higher. 

Sodium nitrate is used as a fertiliser and in a number of industrial processes. In the period from 1880—1910 it accounted for 60% of the world fertiliser nitrogen production. In the 1990s sodium nitrate accounts for 0.1% of the world fertiliser nitrogen production, and is used for some specific crops and soil conditions. This decline has resulted from an enormous growth in fertiliser manufacture and an increased use of less expensive nitrogen fertilisers (qv) produced from synthetic ammonia (qv), such as urea (qv), ammonium nitrate, ammonium phosphates, ammonium sulfate, and ammonia itself (see Ammonium compounds). The commercial production of synthetic ammonia began in 1921, soon after the end of World War I. The main industrial market for sodium nitrate was at first the manufacture of nitric acid (qv) and explosives (see Explosives and propellants). As of the mid-1990s sodium nitrate was used in the production of some explosives and in a number of industrial areas. 

Organic Reactions. Primary alcohols react with sulfamic acid to form alkyl ammonium sulfate salts (21—23) ... 

Sulfation by sulfamic acid has been used ia the preparation of detergents from dodecyl, oleyl, and other higher alcohols. It is also used ia sulfating phenols and phenol—ethylene oxide condensation products. Secondary alcohols react ia the presence of an amide catalyst, eg, acetamide or urea (24). Pyridine has also been used. Tertiary alcohols do not react. Reactions with phenols yield phenyl ammonium sulfates. These reactions iaclude those of naphthols, cresol, anisole, anethole, pyrocatechol, and hydroquinone. Ammonium aryl sulfates are formed as iatermediates and sulfonates are formed by subsequent rearrangement (25,26). 

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