Ammonia Early Process Development

Large single-train natural gas feed plants are also be--coming prominent in fertilizer production in the devel- 

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Fauser An early process for making ammonia. Developed by G. Fauser in Italy in 1924. 

Feld Also called Thionite. An early process proposed for removing hydrogen sulfide and ammonia from coal gas by absorption in an aqueous solution of ammonium thionates. Investigated by W. Feld in Germany in the early 1900s operated at Konigsberg, but never fully developed. 

Frank-Caro Also called the Cyanamide process. An early process for fixing atmospheric nitrogen. Lime and carbon were heated to produce calcium carbide this was reacted with nitrogen to give calcium cyanamide, which was hydrolyzed with steam to yield ammonia and calcium carbonate. Developed by A. Frank and N. Caro from 1895 at Dynamit, Germany, and used in Germany, Norway, and Italy until it was replaced by the Haber-Bosch process after World War I. 

Researchers returned to the oxidation of ammonia in air, (recorded as early as 1798) in an effort to improve production economics. In 1901 Wilhelm Ostwald had first achieved the catalytic oxidation of ammonia over a platinum catalyst. The gaseous nitrogen oxides produced could be easily cooled and dissolved in water to produce a solution of nitric acid. This achievement began the search for an economic process route. By 1908 the first commercial facility for production of nitric acid, using this new catalytic oxidation process, was commissioned near Bochum in Germany. The Haber-Bosch ammonia synthesis process came into operation in 1913, leading to the continued development and assured future of the ammonia oxidation process for the production of nitric acid. 

Coupled transport was the first carrier facilitated process developed, originating in early biological experiments involving natural carriers contained in cell walls. As early as 1890, Pfeffer postulated that the transport in these membranes involved carriers. Perhaps the first coupled transport experiment was performed by Osterhout, who studied the transport of ammonia across algae cell walls [1], A biological explanation of the coupled transport mechanism in liquid membranes is shown in Figure 11.2 [2],... 

Some other early processes for making ammonia are listed below along with some ammonia process developments from the 1980 s and 1990 s ... 

The development of a practical ammonia synthesis process in the early years of the twentieth century was a profound scientific achievement of great social significance in view of the subsequent dependence of the world on fertilizer for support of its growing population. 

Improvements made to the process by Nippon Steel during the early 1970s were described by Kozumi et al. (1977). One important new feature was the possible use of ammonia as the alkaline component of the solution in addition to sodium carbonate. This led to the development of two parallel technologies the Ammonia-Takahax and the Sodium-Takahax proces.s-es. The application of the Ammonia-Takahax process is preferred when the feed gas contains sufficient ammonia, and ammonium sulfate is the desired byproduct. The Sodium-Takahax process is preferred when either elemental sulfur or sulfuric acid is the desired byproduct (GEESl, 1981). 

Over 95 percent of the 11 million tons of nitrogen supplied to U.S. farmers yearly in commercial fertilizers originates as synthetic ammonia made from air, water, and either a petroleum-based hydrocarbon or coal. The development of a practical ammonia synthesis process in the early years of the twentieth century was a profound scientific achievement of great social significance, in view of the subsequent dependence of the world on fertilizer for support of its growing population. 

Andrussow Process. This process, developed by Dr. L. Andrussow in Germany in the early 1930s, has been the major process for large-scale HCN manufacture for the last three decades. (See Fig. 28.30.) The reaction of ammonia with methane to form HCN is as follows ... 

The Haber-Bosch ammonia synthesis process led to similar developments in other European countries and the US. As a result, many other commercial processes were being operated during the 1920s. Production rates were very small compared with modem plants but an extremely wide range of operating conditions was introduced together with a number of different catalysts. Despite these initial differences, most plants built in recent years still operate with more or less the same conditions as those chosen for the first BASF process. Some of the early ammonia processes are listed in Table 10.3. 

Phosphonium Salt—Urea Precondensate. A combination approach for producing flame-retardant cotton-synthetic blends has been developed based on the use of a phosphonium salt—urea precondensate (145). The precondensate is appUed to the blend fabric from aqueous solution. The fabric is dried, cured with ammonia gas, and then oxidized. This forms a flame-resistant polymer on and in the cotton fibers of the component. The synthetic component is then treated with either a cycUc phosphonate ester such as Antiblaze 19/ 19T, or hexabromocyclododecane. The result is a blended textile with good flame resistance. Another patent has appeared in which various modifications of the original process have been claimed (146). Although a few finishers have begun to use this process on blended textiles, it is too early to judge its impact on the industry. 

Even though form amide was synthesized as early as 1863 by W. A. Hoffmann from ethyl formate [109-94-4] and ammonia, it only became accessible on a large scale, and thus iadustrially important, after development of high pressure production technology. In the 1990s, form amide is mainly manufactured either by direct synthesis from carbon monoxide and ammonia, or more importandy ia a two-stage process by reaction of methyl formate (from carbon monoxide and methanol) with ammonia. 

Early in the twentieth century, the first attempts to manufacture formamide directiy from ammonia and carbon monoxide under high temperature and pressure encountered difficult technical problems and low yields (23). Only the introduction of alkaU alkoxides in alcohoHc solution, ie, the presence of alcoholate as a catalyst, led to the development of satisfactory large-scale formamide processes (24). 

Reciprocating Compressors. Prior to 1895, when Linde developed his air Hquefaction apparatus, none of the chemical processes used industrially required pressures much in excess of I MPa (145 psi) and the need for a continuous supply of air at 20 MPa provided the impetus for the development of reciprocating compressors. The introduction of ammonia, methanol, and urea processes in the early part of the twentieth century, and the need to take advantage of the economy of scale in ammonia plants, led to a threefold increase in the power required for compression from 1920 to 1940. The development of reciprocating compressors was not easy Htfle was known about the effects of cycles of fluctuating pressure on the behavior of the... 

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