Production of Ammonia

History of ammonia manufacturing processes

Before the start of World War I, most ammonia was obtained by the dry distillation of nitrogenous vegetable and animal products; the reduction of nitrous acid and nitrites with hydrogen; and the decomposition of ammonium salts by alkaline hydroxides or by quicklime, the salt most generally used being the chloride (sal-ammoniac). The Haber process, which is the production of ammonia by combining hydrogen and nitrogen, was first patented by Fritz Haber in 1908. In 1910, Carl Bosch, while working for the German chemical company BASF, successfully commercialized the process and secured further patents. It was first used on an industrial scale by the Germans during World War I. Since then, the process has often been referred to as the Haber-Bosch process.

Industrial Uses
Fertilizers Explosives Food and beverages Industry Metal Treating Mining Industry Refrigerant Rubber Industry

Haber-Bosch process
This process involves the direct reaction between Hydrogen and Nitrogen. Before carrying out the process, Nitrogen and Hydrogen gas are produced.

Nitrogen
Nitrogen is by far the most abundant gas in the Earth's atmosphere, making up 78.084% of the air we breathe. Nitrogen is commonly produced industrially by the low-temperature distillation of air.

Hydrogen
Hydrogen can be produced by either of these various processes, Reforming Methane Reforming Methanol Electrolysis of water Hydrogen is commonly produced on an industrial large scale by the catalytic reforming of Methane. Although hydrogen can also be produced by catalytically reforming of methanol or by the electrolysis of water, neither of those processes are currently practiced on a large scale.

Reaction
This involves the direct combination of Nitrogen and Hydrogen. The reaction is reversible, meaning that some ammonia will be formed, but not all will react. The reaction is as follows, N2(g) + 3H2(g) 2NH3(g) H = -93.6 kJ/mol

Process Flow Diagram

Modern Ammonia Process Flow Diagram

The first step in the process is to remove sulfur compounds from the feedstock because sulfur deactivates the catalysts used in subsequent steps. Sulfur removal requires catalytic hydrogenation to convert sulfur compounds in the feedstocks to gaseous hydrogen sulfide: H2 + RSH RH + H2S

The gaseous hydrogen sulfide is then absorbed and removed by passing it through beds of zinc oxide where it is converted to solid zinc sulfide: H2S + ZnO ZnS + H2O

Catalytic steam reforming of the sulfur-free feedstock is then used to form hydrogen plus carbon monoxide: CH4 + H2O CO + 3H2

The next step uses catalytic shift conversion to convert the carbon monoxide to carbon dioxide and more hydrogen: CO + H2O CO2 + H2

The carbon dioxide is then removed either by absorption in aqueous ethanolamine solutions or by adsorption in Pressure Swing Adsorbers (PSA) using proprietary solid adsorption media. The final step in producing the hydrogen is to use catalytic methanation to remove any small residual amounts of carbon monoxide or carbon dioxide from the hydrogen: CO + 3H2 CO2 + 4H2 CH4 + H2O CH4 + 2H2O

To produce the desired end-product ammonia, the hydrogen is then catalytically reacted with nitrogen (derived from process air) to form anhydrous liquid ammonia. This step is known as the ammonia synthesis loop. 3H2 + N2 2NH3

The steam reforming, shift conversion, carbon dioxide removal and methanation steps each operate at absolute pressures of about 25 to 35 bar, and the ammonia synthesis loop operates at absolute pressures ranging from 60 to 180 bar, depending on the proprietary design used.