Carbon monoxide ammonia synthesis

J.P.Picard M.Blais A New Approach to the Synthesis of Calcium Cyanamide without Using Electrical PowerM> PATR 2261 (1955) (Conf) 14)Sax (1957), 426 WJ.P. Picard V.LSiele, "Mechanism of Formation of White Calcium Cyanamide by the Picatinny Process . PATR 2405 (1957) (Conf) l6)J.P. Picard et al, "Laboratory Pilot Plant Investigation of Picatinny Process for Producing White Calcium Cyanamide , PATR 2452 (1957) (Conf) 17)V.I.Siele et al, "Suitability of White Calcium Cyanamide for the Preparation of Guanidine Nitrate , PATR 2455 (1957) (Conf) 18)M.Blais J.P.Picard, "Effect of Various Physical Properties of Lime on the Purity of White Calcium Cyanmide Made by the Picatinny Process , PATR 2457 (1857) (Conf) 19)S. Chard et al, "The Manufacture of Calcium Cyanamide Via Carbon Monoxide, Ammonia and Reactive Lime Parti. Laboratory Work ERDE Rept 2/R/57 (1957) (Conf), and "Part II. An Assessment of the Possible Procedure... 

Shultz, Seligman, Shaw, and Anderson (5) attempted to prepare nitrides by treating raw (oxide) iron catalysts directly with ammonia. An analogous reaction, the formation of iron carbides by treatment of raw precipitated catalysts with carbon monoxide or synthesis gas, can be carried out at temperatures between 200° and 325°C. However, ammonia treatment of a precipitated catalyst (Fe203-Cu0-K2C03, Bureau of Mines number P3003.24) at 300°, 350°, and 400°C. resulted... 

The Rectisol process is very flexible and can be configured to address the separation of synthesis gas into various components, depending on the final products that are desired from the gas. It is very suitable to complex schemes where a combination of products is needed, for example, hydrogen, carbon monoxide, ammonia and methanol synthesis gases, and fuel gas sidestreams. 

Takano, Y. Ohashi, A. Kaneko T. Kobayashi, K. Abiotic synthesis of high-molecular-weight organics from an inorganic gas mixture of carbon monoxide, ammonia and water by 3 MeV proton irradiation. Appl. Phys. Lett. 2004, 84, 1410-1412. 

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. 

Two-Step Process. The significant advantage of the two-step process is that it only requkes commercial-grade methyl formate and ammonia. Thus the cmde product leaving the reactor comprises, in addition to excess starting materials, only low boiling substances, which are easily separated off by distillation. The formamide obtained is of sufficient purity to meet all quaUty requkements without recourse to the costiy overhead distillation that is necessary after the dkect synthesis from carbon monoxide and ammonia. 

The estimated capacity of formamide was approximately 100,000 t/yr worldwide in 1990. In 1993, there are only three significant producers BASE in Germany is the leading manufacturer. Smaller quantities of formamide are produced in the former Czechoslovakia (Sokolov) and Japan (Nitto) by direct synthesis from carbon monoxide and ammonia. Most of the formamide produced is utilized direcdy by the manufacturers. The market price for formamide (ca 1993) is about 2.00/kg. 

Methane. The largest use of methane is for synthesis gas, a mixture of hydrogen and carbon monoxide. Synthesis gas, in turn, is the primary feed for the production of ammonia (qv) and methanol (qv). Synthesis gas is produced by steam reforming of methane over a nickel catalyst. 

Reforming is completed in a secondary reformer, where air is added both to elevate the temperature by partial combustion of the gas stream and to produce the 3 1 H2 N2 ratio downstream of the shift converter as is required for ammonia synthesis. The water gas shift converter then produces more H2 from carbon monoxide and water. A low temperature shift process using a zinc—chromium—copper oxide catalyst has replaced the earlier iron oxide-catalyzed high temperature system. The majority of the CO2 is then removed. 

Pyrrohdinone (2-pyrrohdone, butyrolactam or 2-Pyrol) (27) was first reported in 1889 as a product of the dehydration of 4-aminobutanoic acid (49). The synthesis used for commercial manufacture, ie, condensation of butyrolactone with ammonia at high temperatures, was first described in 1936 (50). Other synthetic routes include carbon monoxide insertion into allylamine (51,52), hydrolytic hydrogenation of succinonitnle (53,54), and hydrogenation of ammoniacal solutions of maleic or succinic acids (55—57). Properties of 2-pyrrohdinone are Hsted in Table 2. 2-Pyrrohdinone is completely miscible with water, lower alcohols, lower ketones, ether, ethyl acetate, chloroform, and benzene. It is soluble to ca 1 wt % in aUphatic hydrocarbons. 

Ammonia production from natural gas includes the following processes desulfurization of the feedstock primary and secondary reforming carbon monoxide shift conversion and removal of carbon dioxide, which can be used for urea manufacture methanation and ammonia synthesis. Catalysts used in the process may include cobalt, molybdenum, nickel, iron oxide/chromium oxide, copper oxide/zinc oxide, and iron. 

The reaction produces additional hydrogen for ammonia synthesis. The shift reactor effluent is cooled and tlie condensed water is separated. The gas is purified by removing carbon dioxide from the synthesis gas by absorption with hot carbonate, Selexol, or methyl ethyl amine (MEA). After purification, the remaining traces of carbon monoxide and carbon dioxide are removed in the methanation reactions. 

The second step after secondary reforming is removing carbon monoxide, which poisons the catalyst used for ammonia synthesis. This is done in three further steps, shift conversion, carbon dioxide removal, and methanation of the remaining CO and CO2. 

Subsequent studies have failed to support the carbide theory, and it is now generally accepted that carbides of the type proposed by Craxford play little or no part in the Fischer-Tropsch synthesis (86, 87). It has, however, recently been suggested, by analogy with the mechanism proposed for the Haber synthesis of ammonia, that carbides formed by dissociative absorption of carbon monoxide would be expected to be readily hydrogenated and could therefore be of importance in Fischer-Tropsch synthesis over heterogeneous catalyst (88). 

Synthesis activities, EIA, 70 236 Synthesis gas (syngas), 73 766, 77 763 in ammonia synthesis, 2 695-701 carbon monoxide manufacture, 5 ... 

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