Reaction rate and equilibrium [edit]

Nitrogen (N2) is very unreactive because the molecules are held together by strong triple bonds. The Haber process relies on catalysts that accelerate the scission of this triple bond. Two opposing considerations are relevant to this synthesis: the position of the equilibrium and the rate of reaction. At room temperature, the equilibrium is strongly in favor of ammonia, but the reaction doesn't proceed at a detectable rate. The obvious solution is to raise the temperature, but because the reaction is exothermic, the equilibrium constant (using atm units) becomes 1 around 150 or 200C. (See Le Chatelier's principle.) Variation in Keq for the equilibrium Above this temperature, the equilibrium quickly N2 (g) + 3H2 (g) 2NH3 (g) becomes quite unfavourable at atmospheric pressure, as a function of temperature[12] according to the Van't Hoff equation. Thus one might Temperature (C) Keq suppose that a low temperature is to be used and some 300 4.34 x 103 other means to increase rate. However, the catalyst itself requires a temperature of at least 400 C to be efficient. 400 1.64 x 104 Pressure is the obvious choice to favour the forward reaction because there are 4 moles of reactant for every 2 moles of product (see entropy), and the pressure used (around 200 atm) alters the equilibrium concentrations to give a profitable yield.[citation needed] 450 500 550 600 4.51 x 105 1.45 x 105 5.38 x 106 2.25 x 106

Economically, though, pressure is an expensive commodity. Pipes and reaction vessels need to be strengthened, valves more rigorous, and there are safety considerations of working at 200 atm. In addition, running pumps and compressors takes considerable energy. Thus the compromise used gives a single pass yield of around 15%.[citation needed] Another way to increase the yield of the reaction would be to remove the product (i.e. ammonia gas) from the system. In practice, gaseous ammonia is not removed from the reactor itself, since the temperature is too high; but it is removed from the equilibrium mixture of gases leaving the reaction vessel. The hot gases are cooled enough, whilst maintaining a high pressure, for the ammonia to condense and be removed as liquid. Unreacted hydrogen and nitrogen gases are then returned to the reaction vessel to undergo further reaction.[citation needed]

Catalysts [edit]
The most popular catalysts are based on iron promoted with K2O, CaO, SiO2, and Al2O3. The original HaberBosch reaction chambers used osmium as catalysts. However, under Bosch's direction in 1909, the BASF researcher Alwin Mittasch discovered a much less expensive iron-based catalyst, which is still used today. Part of the industrial production utilizes ruthenium rather than an iron-based catalysts (the KAAP process). Ruthenium forms more active catalysts that allows milder operating pressures. Such catalysts are prepared by decomposition of triruthenium dodecacarbonyl on graphite.[1] In industrial practice, the iron catalyst is prepared by exposing a mass of magnetite, an iron oxide, to the hot hydrogen feedstock. This reduces some of the magnetite to metallic iron,

removing oxygen in the process. However, the catalyst maintains most of its bulk volume during the reduction, and so the result is a highly porous material whose large surface area aids its effectiveness as a catalyst. Other minor components of the catalyst include calcium and aluminium oxides, which support the porous iron catalyst and help it maintain its surface area over time, and potassium, which increases the electron density of the catalyst and so improves its activity. The reaction mechanism, involving the heterogeneous catalyst, is believed to involve the following steps: 1. 2. 3. 4. 5. 6. N2 (g) N2 (adsorbed) N2 (adsorbed) 2 N (adsorbed) H2(g) H2 (adsorbed) H2 (adsorbed) 2 H (adsorbed) N (adsorbed) + 3 H(adsorbed) NH3 (adsorbed) NH3 (adsorbed) NH3 (g)

Reaction 5 occurs in three steps, forming NH, NH2, and then NH3. Experimental evidence points to reaction 2 as being the slow, rate-determining step. A major contributor to the elucidation of this mechanism is Gerhard Ertl.[13] Steam reforming: CnHm + n H2O (n + m/2) H2 + n CO Methanation: CO + 3 H2 CH4 + H2O Water-gas shift: CO + H2O H2 + CO2

Industrial reforming [edit]

Main article: Methane reformer

Steam reforming of natural gas or syngas sometimes referred to as steam methane reforming (SMR) is the most common method of producing commercial bulk hydrogen as well as the hydrogen used in the industrial synthesis of ammonia. It is also the least expensive method.[4] At high temperatures (700 1100 C) and in the presence of a metal-based catalyst (nickel), steam reacts with methane to yield carbon monoxide and hydrogen. These two reactions are reversible in nature.
CH4 + H2O CO + 3 H2

Additional hydrogen can be recovered by a lower-temperature gas-shift reaction with the carbon monoxide produced. The reaction is summarized by:
CO + H2O CO2 + H2

The first reaction is strongly endothermic (consumes heat), the second reaction is mildly exothermic (produces heat). The United States produces nine million tons of hydrogen per year, mostly with steam reforming of natural gas. The worldwide ammonia production, using hydrogen derived from steam reforming, was 109 million metric tonnes in 2004.[5] This SMR process is quite different from and not to be confused with catalytic reforming of naphtha, an oil refinery process that also produces significant amounts of hydrogen along with high octane gasoline. The efficiency of the process is approximately 65% to 75%.[ 2.1 STEAM/ CARBON SENSITIVITY Primary reformer inlet steam-to-carbon (s/c) ratio is an important factor in reformer design. The literature advises the maintenance of a relatively high s/c ratio to prevent mechanical as well as economic problems during the life of the plant. Higher s/c ratios are more effective for a number of reasons. First, because a high s/c ratio favors the products in the reforming reaction equilibrium, it lowers the amount of unreacted methane, or methane slip, out of the secondary reformer and increases the production of hydrogen. Second, a high s/c ratio inhibits the occurence of carbon-forming side reactions in the primary reformer that result in carbon deposits on the catalyst. Carbon deposition increases the resistance to gas flow in the primary reformer tubes and may impair catalyst activity. This impairment lowers the rate of the reforming reaction and can cause local overheating or "hot bands" in reformer tubes that result in premature tube wall failure. Finally, a high s/c ratio provides the necessary steam for the shift conversion of carbon monoxide and reduces the risk of carburization damage to the tube material [3]. Table 2 shows process sensitivity to s/c ratio. A 3.0/1.0 s/c ratio was found to be the most optimum ratio for the purposes of this process. Sensitivity runs in Aspen showed that 4.0/1.0 s/c ratio requires a larger heat duty than a 3.0/1.0 ratio. This increases cost as more heat has to be applied to the process. However, lowering the s/c ratio to 2.5/1.0 was found to increase methane slip significantly, decreasing the amount of hydrogen produced. For these reasons a 3.0/1.0 s/c ratio was chosen. 1.0 INTRODUCTION Primary and secondary reformers play an important role in the production of ammonia. The goal of reforming is to prepare as pure as possible a gas mixture of nitrogen and hydrogen in a 3:1 stoichiometric ratio from the raw materials of water, air, and natural gas. The reactions by which this ratio are achieved are given as follows:

Reaction 1, the steam reforming reaction, and reaction 2, the water gas shift reaction, are endothermic and occur in the primary reformer. Reaction 3, the combustion reaction, is

exothermic and occurs along with reactions 1 and 2 in the secondary reformer [1]. Optimization of the reforming process involves the manipulation of parameters to achieve high process yield while maintaining low operating and installed costs. The parameters which are monitered in this design include temperature, pressure, steam to carbon ratio, and percent oxyegen in the air feed.