Ammonia, production

Carbon dioxide, COj. Sublimes — 78 5 C. A colourless gas at room temperature, occurs naturally and plays an important part in animal and plant respiration. Produced by the complete combustion of carbon-containing materials (industrially from flue gases and from synthesis gas used in ammonia production) and by heating metal carbonates or by... 

The technology of urea production is highly advanced. The raw materials requited ate ammonia and carbon dioxide. Invariably, urea plants ate located adjacent to ammonia production faciUties which conveniently furnish not only the ammonia but also the carbon dioxide, because carbon dioxide is a by-product of synthesis gas production and purification. The ammonia and carbon dioxide ate fed to a high pressure (up to 30 MPa (300 atm)) reactor at temperatures of about 200°C where ammonium carbamate [111-78-0] CH N202, urea, and water ate formed. 

Coal is expected to be the best domestic feedstock alternative to natural gas. Although coal-based ammonia plants have been built elsewhere, there is no such plant in the United States. Pilot-scale projects have demonstrated effective ammonia-from-coal technology (102). The cost of ammonia production can be anticipated to increase, lea ding to increases in the cost of producing nitrogen fertilizers. 

This excess hydrogen is normally carried forward to be compressed into the synthesis loop, from which it is ultimately purged as fuel. Addition of by-product CO2 where available may be advantageous in that it serves to adjust the reformed gas to a more stoichiometric composition gas for methanol production, which results in a decrease in natural gas consumption (8). Carbon-rich off-gases from other sources, such as acetylene units, can also be used to provide supplemental synthesis gas. Alternatively, the hydrogen-rich purge gas can be an attractive feedstock for ammonia production (9). 

The mature Haber-Bosch technology is unlikely to change substantiaHy in the foreseeable future. The centers for commercial ammonia production may, however, relocate to sites where large quantities of natural gas are flared from cmde oil production, eg, Saudi Arabia or Venezuela. Relocation would not offset the problems for agriculture of high transportation and storage costs for ammonia production and distribution. Whereas the development of improved lower temperature and pressure catalysts is feasible, none is on the horizon as of this writing. 

Synthesis Gas Preparation Processes. Synthesis gas for ammonia production consists of hydrogen and nitrogen in about a three to one mole ratio, residual methane, argon introduced with the process air, and traces of carbon oxides. There are several processes available for synthesis gas generation and each is characterized by the specific feedstock used. A typical synthesis gas composition by volume is hydrogen, 73.65% nitrogen, 24.55% methane, <1 ppm-0.8% argon, 100 ppm—0.34% carbon oxides, 2—10 ppm and water vapor, 0.1 ppm. 

Fig. 6. Flow sheet for ammonia production from Lurgi coal gasification.

Ammonia production by partial oxidation of hydrocarbon feeds depends to some degree on the gasification step. The clean raw synthesis gas from a Shell partial oxidation system is first treated for sulfur removal, then passed through shift conversion. A Hquid nitrogen scmbbiag step follows. 

Table 6. Energy Required for Ammonia Production based on Feedstock Process, GJ/t...

In the 1980s, however, the prices of oil and natural gas reversed their upward trends. Natural gas discoveries, both on-shore and off-shore, have considerably iacreased the world s energy supply and oil discoveries, many with associated gas, contributed more feedstock potential for ammonia production. 

Ammonia production per se is relatively clean compared to other chemical process industries, and presents no unique environmental problems. Synthesis gas generation is the principal area requiring environmental controls and the nature of the controls depends on the feedstock and method of processing. 

Capacity, Production, and Consumption. Ammonia production has worldwide significance about 85% of the ammonia produced is used for nitrogen fertilizers. As the primary source of fertilizer nitrogen, it is key to solving world food production requkements. The remaining 15% goes into various industrial products such as fibers, animal feeds, explosives, etc. 

Markets. Industrial use of ammonia varies according to region. Eor example, industrial usage represents 20% of the ammonia production in the United States and Western Europe, 10% in the USSR, 1—10% in Asia, and 5% in Latin America and North Africa (79). Fertiliser ammonia consumed domestically in most countries is converted to straight or compound fertilisers such as urea, ammonium nitrate, diammonium phosphate, and various grades of mixed fertilisers. However, almost 29% of ammonia nitrogen in the United States is consumed as direct appHcation material. The use of nitrogen solution such as urea and ammonium nitrate (UAN) has also become popular in the United States and the USSR. 

As can be seen from this analysis, the natural gas feedstock and capital charges amount to over 93% of the total production cost before return on investment. Therefore, energy consumption and capital investment are the key factors in determining ammonia production profitabiUty. 

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. 

T. Sueyama and T. Tsujino, "Ammonia Production by a Coal Gasification Process," British Sulphur Feriiliiyer Symposium, British Sulphur Ltd.,... 

The high capital cost, about 1500/kW, is the principal deterrent to growth of the IGCC concept. The abiUty to remove up to 99% of the sulfur species from the combustion products make the IGCC an environmentally desirable option as make calcium carbide (see Carbides), from which acetjiene is made. Synthesis gas for methanol and ammonia production is also made from gasification of coke. 

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. 

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