Ammonium sulfate by-product

HPO [Hydroxylamine phosphate oxime] A process for making caprolactam, an intermediate in the manufacture of polyamides. It differs from related processes, such as HSO, in producing less of the ammonium sulfate by-product. Developed by DSM Research, The Netherlands, operated by DSM Polymers and Hydrocarbons, and offered for license by Stamicarbon. 

Hydrogen cyanide Tail gases, ammonia, hydrogen cyanide Ammonia Sulfuric acid Ammonia removal while producing ammonium sulfate by-product Stripping not practiced... 

The nickel, cobalt, and zinc in the reduction end solution are precipitated as metal ammonium double salts after solution evaporation to 500 gm/liter ammonium sulfate. The double salts containing the nickel and cobalt centrifuged from the solution are then dissolved in water. Nickel and cobalt are separated by formation of cobaltic pentammine sulfate solution. The cobaltic pentammine solution is reduced at 350°F under hydrogen at 500 psig to produce cobalt powder. The ammonium sulfate by-product is prepared by stripping out the metal values with hydrogen sulfide. 

Other variations of the caprolactam process produce hydroxylamine disulfonic acid which is hydrolyzed to hydroxylamine sulfate and an ammonium sulfate by-product. Additional ammonium sulfate is produced downstream in the oximation step by the reaction of ammonia with sulfuric acid. Ammonium sulfate is a low value by-product and there is an advantage to producing hydroxylamine sulfate directly in order to avoid the production of unwanted ammonium sulfate downstream. The oxygen-based NO reduction process provides this advantage and the processes that use it are characterized as low by-product production processes. 

The advantage over the BASF and CAPROPOL processes is that, overall, it produces less ammonium sulfate by-product. It produces no ammonium sulfate in the oximation reaction, however, ammonium sulfate is still produced downstream in the Beckmann rearrangement step. 

Cominco [Consolidated Mining and Smelting Company] A process for absorbing sulfur dioxide from smelting operations. The sulfur dioxide is absorbed in an aqueous solution of ammonium sulfite regeneration is by acidification with sulfuric acid. The ammonium sulfate by-product is sold. Operated at the Cominco smelter at Trail, Canada, and at other smelters and sulfuric acid plants in the United States. Licensed hy the Olin-Mathieson Corporation. The name has also been applied to a lead extraction process. 

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). 

There is extensive research ongoing for new synthesis processes which are economically favourable due to less expensive reactants or easier processes. One very important point is the avoidance of the production of a large amount of ammonium sulfate, which can be achieved by the prevention of the formation of any salt or by the replacement of ammonium sulfate by another ammonium salt with increased economical value. Recently, studies of Beckmann rearrangement of cyclohexanone oxime in friendly enviionment conditions have received special attention . ... 

The arrangement of the oxime to caprolactam is earned out by oleum, which is then neutralized by ammonia with the production of ammonium sulfate, by the following reaction ... 

Nitration with nitric acid in the presence of strong protic acids such as H2SO4, FSO3H, and CF3SO3H or Lewis acids such as boron trifluotide requires subsequent separation of spent acid (due to water formed in the reaction) and neutralization of acid left in the product. One is generally left with a large amount of dilute acid for disposal, which is neutralized in the case of sulfuric-acid-catalyzed nitrations to a mixture of ammonium nitrate and ammonium sulfate. By using a solid acid catalyst most of these environmental problems can be eliminated. The solid acid catalyst is simply separated and recycled for subsequent use. 

Acetonitrile also is used as a catalyst and as an ingredient in transition-metal complex catalysts (35,36). There are many uses for it in the photographic industry and for the extraction and refining of copper and by-product ammonium sulfate (37—39). It also is used for dyeing textiles and in coating compositions (40,41). It is an effective stabilizer for chlorinated solvents, particularly in the presence of aluminum, and it has some appflcation in... 

In the early versions, ethylene cyanohydrin was obtained from ethylene chlorohydrin and sodium cyanide. In later versions, ethylene oxide (from the dkect catalytic oxidation of ethylene) reacted with hydrogen cyanide in the presence of a base catalyst to give ethylene cyanohydrin. This was hydrolyzed and converted to acryhc acid and by-product ammonium acid sulfate by treatment with about 85% sulfuric acid. 

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. 

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. 

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