The Ammonia Synthesis

Strongin D R, Carrazza J, Bare S R and Somoqai G A 1987 The importance of Cj sites and surface roughness in the ammonia synthesis reaction over iron J. Catal. 103 213... 

Urea is produced from liquid NH and gaseous CO2 at high, pressure and temperature both reactants are obtained from an ammonia-synthesis plant. The latter is a by-product stream, vented from the CO2 removal section of the ammonia-synthesis plant. The two feed components are deUvered to the high pressure urea reactor, usually at a mol ratio >2.5 1. Depending on the feed mol ratio, more or less carbamate is converted to urea and water per pass through the reactor. 

There has been an increasing interest in utilising off-gas technology to produce ammonia. A number of ammonia plants have been built that use methanol plant purge gas, which consists typically of 80% hydrogen. A 1250 t/d methanol plant can supply a sufficient amount of purge gas to produce 544 t/d of ammonia. The purge gas is first subjected to a number of purification steps prior to the ammonia synthesis. 

Because the ammonia synthesis reaction is an equiUbrium, the quantity of ammonia depends on temperature, pressure, and the H2 to-N2 ratio. At 500°C and 20.3 MPa (200 atm), the equiUbrium mixture contains 17.6% ammonia. The ammonia formed is removed from the exit gases by condensation at about —20° C, and the gases are recirculated with fresh synthesis gas into the reactor. The ammonia must be removed continually as its presence decreases both the equiUbrium yield and the reaction rate by reducing the partial pressure of the N2—H2 mixture. 

Synthesis Temperature. Because of the exothermic nature of the ammonia synthesis reaction, higher temperatures increase reaction rates, but the equihbrium amount of ammonia decreases. Thermal degradation of the catalyst also increases with temperature. 

Shift Conversion. Carbon oxides deactivate the ammonia synthesis catalyst and must be removed prior to the synthesis loop. The exothermic water-gas shift reaction (eq. 23) provides a convenient mechanism to maximize hydrogen production while converting CO to the more easily removable CO2. A two-stage adiabatic reactor sequence is normally employed to maximize this conversion. The bulk of the CO is shifted to CO2 in a high... 

Final Purification. Oxygen containing compounds (CO, CO2, H2O) poison the ammonia synthesis catalyst and must be effectively removed or converted to inert species before entering the synthesis loop. Additionally, the presence of carbon dioxide in the synthesis gas can lead to the formation of ammonium carbamate, which can cause fouHng and stress-corrosion cracking in the compressor. Most plants use methanation to convert carbon oxides to methane. Cryogenic processes that are suitable for purification of synthesis gas have also been developed. 

These pioneers understood the interplay between chemical equiUbrium and reaction kinetics indeed, Haber s research, motivated by the development of a commercial process, helped to spur the development of the principles of physical chemistry that account for the effects of temperature and pressure on chemical equiUbrium and kinetics. The ammonia synthesis reaction is strongly equiUbrium limited. The equiUbrium conversion to ammonia is favored by high pressure and low temperature. Haber therefore recognized that the key to a successful process for making ammonia from hydrogen and nitrogen was a catalyst with a high activity to allow operation at low temperatures where the equiUbrium is relatively favorable. 

Ammonia Synthesis. Another weU-understood reaction is the ammonia synthesis ... 

The majority of known elementary steps are bimoleeular, the remainder being unimoleeular or termoleeular. The ammonia synthesis reaetion is known to oeeur by a number of steps rather than as Nj + 3H2 —> 2NH3. 

The compressed synthesis gas is dried, mixed with a recycle stream, and introduced into the synthesis reactor after the recycle compressor. The gas mixture is chilled and liquid ammonia is removed from the secondary separator. The vapor is heated and passed into the ammonia converter. The feed is preheated inside the converter prior to entering the catalyst bed. The reaction occurs at 450-600°C over an iron oxide catalyst. The ammonia synthesis reaction between nitrogen, N2, and hydrogen, Hj, is... 

Ammonium nitrate is manufactured by reacting ammonia with nitric acid. Consider the process shown by Fig. 9.19. First, namral gas is reformed and converted into hydrogen, nitrogen and carbon dioxide. Hydrogen and nitrogen are separated an fed to the ammonia synthesis plant. A fraction of the produced ammonia is employed in nitric acid formation. Ammonia is first oxidized with compressed air then absorbed in water to form nitric acid. Finally nitric acid is reacted with anunonia to oduce ammonium nitrate. 

The production of ammonia is of historical interest because it represents the first important application of thermodynamics to an industrial process. Considering the synthesis reaction of ammonia from its elements, the calculated reaction heat (AH) and free energy change (AG) at room temperature are approximately -46 and -16.5 KJ/mol, respectively. Although the calculated equilibrium constant = 3.6 X 108 at room temperature is substantially high, no reaction occurs under these conditions, and the rate is practically zero. The ammonia synthesis reaction could be represented as follows ... 

Throughout the book we use the terms catalysis, catalyst and catalytic reaction referring to processes which do not involve any net charge transfer, such as e.g. the oxidation of CO on Pt or the ammonia synthesis on Fe ... 

A classical example of promotion is the use of alkalis (K) on Fe for the ammonia synthesis reaction. Coadsorbed potassium (in the form of K20) significantly enhances the dissociative adsorption of N2 on the Fe surface, which is the crucial and rate limiting step for the ammonia synthesis5 (Fig. 2.1). 

Write the equilibrium constant for the ammonia synthesis reaction, reaction C. 

Self-Test 9.7A The equilibrium constant for the ammonia synthesis (reaction C) is K = 41 at 127°C. What is the value of Kc at that temperature ... 

A molecular view of a limiting reactant situation for the ammonia synthesis. To make 4 molecules of INH3 and 6 molecules of... 

To solve a quantitative limiting reactant problem, we identify the limiting reactant by working with amounts in moles and the stoichiometric coefficients from the balanced equation. For the ammonia synthesis, if we start with 84.0 g of molecular nitrogen and 24.2 g of molecular hydrogen, what mass of ammonia can be prepared First, convert from... 

C15-0007. State the relative rates for the consumption of starting materials and the formation of products for the ammonia synthesis. 

As an indispensable source of fertilizer, the Haber process is one of the most important reactions in industrial chemistry. Nevertheless, even under optimal conditions the yield of the ammonia synthesis in industrial reactors is only about 13%. This Is because the Haber process does not go to completion the net rate of producing ammonia reaches zero when substantial amounts of N2 and H2 are still present. At balance, the concentrations no longer change even though some of each starting material is still present. This balance point represents dynamic chemical equilibrium. 

As an example of how these expressions are used in practical situations, we will calculate the extent to which the ammonia synthesis reaction... 

In our calculation we assume that the gas mixture approaches equilibrium under conditions where the pressure is constant. This situation corresponds, for instance, to a volume of gas moving through a plug flow reactor with a negligible pressure drop. (Note that if the ammonia synthesis were carried out in a closed system, the pressure would decrease with increasing conversion.)... 

Using Eq. (32) for the ammonia synthesis and assuming ideal gas behavior, we immediately obtain... 

Figure 7.21 shows the results for the ammonia synthesis on real catalysts in a reactor. The surface is predominantly covered by atomic nitrogen and by NH intermediates. This actually limits the rate of the reaction as soon as an appreciable partial pressure of ammonia has built up. In fact, ammonia poisons the reaction. 

The kinetics of the ammonia synthesis have been discussed as an example of micro-kinetic modeling in Chapter 7. Here we present a brief description of the process, concentrating on how process variables are related to the microscopic details and the optimization of the synthesis. 

Figure 8.19. The energy consumption of the ammonia synthesis has decreased steadily and is now comparable with the natural process. (Courtesy of HaldorTopsoe AS.)...

Oxygen-containing molecules cannot be tolerated in the ammonia synthesis, primarily because they form iron oxide that blocks the active surface. First the CO2 is removed, through a scrubber, by reaction with a strong base. The remaining CO (and CO2) is then removed by the methanation reaction, converting the CO into methane and water. Finally the water is removed by, for example, molecular sieves. Methane does not present problems because it interacts weakly with the catalyst surface. The gas mixture (Tab. 8.6) is compressed to the roughly 200 bar needed for ammonia synthesis and admitted to the reactor. 

Table 8.6. Typical composition of the feed gas when it enters the ammonia synthesis reactor.

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