Nitrogen Industries Fixed nitrogen from air- major ingredient of fertilizers for making intensive production possible Ammonia-

base from which virtually all nitrogen-containing products are derived History Priestly and Cavendish- produced nitrated by dissolving the oxides of nitrogen thus formed in alkalies, passed electric sparks through air. *nitrogen has been fixed as calcium cyanide, but the process is too expensive except for producing chemicals requiring the cyanamide configuration. Other processes: Thermal processing to mixed oxides of nitrogen (NOX) Cyanide formation Aluminum nitride formation Decomposition of ammonia

Haber and Nernst- studies of equilibrium between nitrogen and hydrogen under pressure to form ammonia and discovered several suitable catalysts. Haber and Bosch- processes for obtaining inexpensive pure hydrogen and nitrogen by workable processes. Commercial high-pressure synthesis of ammonia by 1913 Uses and Economics Ammonia- most important nitrogenous material Made synthetically but some continuous to be obtained as by-product.

Chilean saltpeter (NaNO3)- source of fixed nitrogen. Use of Ammonia Gas Fertilizer Heat treating Paper pulping Nitric acid Nitrate manufacture Explosives of various types Refrigerant

Amines, amides and miscellaneous other organic compounds- derived from ammonia

Raw materials: air, water, hydrocarbons and power *coal can replace hydrocarbon but it is more expensive and the process is more complex. Synthetic Ammonia Ammonia- major raw material Reaction and Equilibriums: ( ) Rates and Catalysts of Reaction: *Ammonia catalysts of several types have been testes, but plants now use iron with added promoters: - Oxides of aluminum - Zirconium - Silicon at about 3% concentrations - Potassium oxide at about 1% *prevent sintering and make the catalyst more porous * Iron catalysts lose their activity rapidly if heated above 520C * Catalysts are also deactivated by contact with copper, phosphorous, arsenic, sulfur and carbon monoxide, which alter the iron composition. Space Velocity- volume of gases, corrected to standard conditions (0Cand 10kPa) that pass over one volume of catalysts per unit time. MANUFACTURING PROCEDURES: 1. 2. 3. 4. 5. 6. Manufacture of reactant gas Purification Compression Catalytic reaction Recovery of ammonia formed Recirculation ( )

Synthesis System:

Ammonia synthesis gas- prepared by high-pressure catalytic reforming hydrocarbon feed, usually natural gas freed of sulfur, in the presence of steam over a nickel catalyst in the primary reformer, then subjected to catalytic shift at a lower temperature in the presence of air. Purpose of shift reaction: 1. Produces more hydrogen per unit of fuel 2. Oxidizes much of the carbon monoxide to the more easily removed carbon dioxide Guard catalysts- captures sulfur and chlorine poison and extend the main catalysts life over 100%. Methane- an inert gas with respect to the ammonia catalyst Refrigeration or Absorption- recovery of ammonia Ammonium Nitrate Ammonium Nitrate- very important nitrogenous fertilizer because of high nitrogen content (33%) Simplicity and cheapness of its manufacture Valuable combination of quick-acting nitrate Slower- acting ammoniacal nitrogen