Synthesis reaction Equilibrium concentrations

Essential for synthesis considerations is the abiUty to determine the amount of ammonia present ia an equiUbrium mixture at various temperatures and pressures. ReHable data on equiUbrium mixtures for pressures ranging from 1,000 to 101,000 kPa (10 —1000 atm) were developed early on (6—8) and resulted ia the determination of the reaction equiUbrium constant (9). Experimental data iadicates that is dependent not only on temperature and pressure, but also upon the ratio of hydrogen and nitrogen present. Table 3 fists values for the ammonia equilibrium concentration calculated for a feed usiag a 3 1 hydrogen to nitrogen ratio and either 0 or 10% iaerts (10). 

A low-pressure process has been developed by ICl operating at about 50 atm (700 psi) using a new active copper-based catalyst at 240°C. The synthesis reaction occurs over a bed of heterogeneous catalyst arranged in either sequential adiabatic beds or placed within heat transfer tubes. The reaction is limited by equilibrium, and methanol concentration at the converter s exit rarely exceeds 7%. The converter effluent is cooled to 40°C to condense product methanol, and the unreacted gases are recycled. Crude methanol from the separator contains water and low levels of by-products, which are removed using a two-column distillation system. Figure 5-5 shows the ICl methanol synthesis process. 

CO in the synthesis gas mixture for the methanol synthesis does not seem to take part directly in the reaction, but it does influence the process through two effects First the water-gas shift reaction and, secondly, through its effect on the surface morphology (and possibly also composition). For thermodynamic reasons, however, it would be desirable if CO could be hydrogenated directly via Eq (18) instead of going through two coupled equations (3) and (19), since it would yield a higher equilibrium concentration of methanol at the reactor exit. 

Since the beginning of the 20th century, organic solvents have been used in enzymatic reaction media [30]. Biocatalytic reactions in water-organic biphasic media were first carried out by Cremonesi et al. [31] and by Buckland et al. [32] less than 30 years ago. Their work aimed at the conversion of high concentrations of poorly water soluble components, particularly steroids. Later, biphasic systems were used for enzyme-catalyzed synthesis reactions that were unfavored in water, changing the reaction equilibrium towards the higher yield of the product, such as esters or peptides. 

When produced from natural gas the synthesis gas will be impure, containing up to 5 per cent inerts, mainly methane and argon. The reaction equilibrium and rate are favoured by high pressure. The conversion is low, about 15 per cent and so, after removal of the ammonia produced, the gas is recycled to the converter inlet. A typical process would consist of a converter (reactor) operating at 350 bar a refrigerated system to condense out the ammonia product from the recycle loop and compressors to compress the feed and recycle gas. A purge is taken from the recycle loop to keep the inert concentration in the recycle gas at an acceptable level. 

Figure 17.20. Control of temperature in multibed reactors so as to utilize the high rates of reaction at high temperatures and the more favorable equilibrium conversion at lower temperatures, (a) Adiabatic and isothermal reaction lines on the equilibrium diagram for ammonia synthesis, (b) Oxidation of SOz in a four-bed reactor at essentially atmospheric pressure, (c) Methanol synthesis in a four bed reactor by the ICI process at 50 atm not to scale 35% methanol at 250°C, 8.2% at 300°C, equilibrium concentrations.

In the early 1900s, the German chemist Fritz Haber discovered that a catalyst consisting of iron mixed with certain metal oxides causes the reaction to occur at a satisfactory rate at temperatures where the equilibrium concentration of NH3 is reasonably favorable. The yield of NH3 can be improved further by running the reaction at high pressures. Typical reaction conditions for the industrial synthesis of ammonia are 400-500°C and 130-300 atm. 

In former technical processes for the synthesis of nitric oxide, the reaction gases had to be rapidly cooled below 725 K. Slow cooling would give the equilibrium concentration of nitric oxide at the appropriate temperature. At temperatures lower than 725 K, nitric oxide is metastable and does not decompose to dinitrogen and dioxygen. Careful control of the... 

The law of mass action is widely applicable. It correctly describes the equilibrium behavior of all chemical reaction systems whether they occur in solution or in the gas phase. Although, as we will see later, corrections for nonideal behavior must be applied in certain cases, such as for concentrated aqueous solutions and for gases at high pressures, the law of mass action provides a remarkably accurate description of all types of chemical equilibria. For example, consider again the ammonia synthesis reaction. At 500°C the value of K for this reaction is 6.0 X 10 2 F2/mol2. Whenever N2, H2, and NH3 are mixed together at this temperature, the system will always come to an equilibrium position such that... 

For the ammonia synthesis reaction, the equilibrium expression can be written in terms of concentrations,... 

When the reactants and products of a given chemical reaction are mixed, it is useful to know whether the mixture is at equilibrium and, if it is not, in which direction the system will shift to reach equilibrium. If the concentration of one of the reactants or products is zero, the system will shift in the direction that produces the missing component. However, if all the initial concentrations are not zero, it is more difficult to determine the direction of the move toward equilibrium. To determine the shift in such cases, we use the reaction quotient (Q). The reaction quotient is obtained by applying the law of mass action, but using initial concentrations instead of equilibrium concentrations. For example, for the synthesis of ammonia,... 

In Example 6.3 we were able to solve for the unknown by taking the square root of both sides of the equation. However, this situation is not very common, so we must now consider a more typical problem. Suppose that for a synthesis of hydrogen fluoride from hydrogen and fluorine, 3.000 moles of H2 and 6.000 moles of F2 are mixed in a 3.000-liter flask. The equilibrium constant for the synthesis reaction at this temperature is 1.15 X 102. We calculate the equilibrium concentration of each component as follows ... 

To see how we can predict the effects of a change in concentration on a system at equilibrium, we will consider the ammonia synthesis reaction. Suppose there is an equilibrium position described by these concentrations ... 

Thermodynamically, the reforming reaction, Equation 3.5.1, shows that the reformer should be operated at the lowest pressure and highest temperature possible. The reforming reaction occurs on a nickel-oxide catalyst at 880 °C (1620 °F) and 20 bar, which results in a 25 °C approach to the equilibrium temperature [25,29]. Methane conversion increases by reducing the pressure, but natural gas is available at a high pressure. It would be costly to reduce the reformer pressure and then recompress the synthesis gas later to 100 bar (98.7 atm) for the converter. The steam to carbon monoxide ratio is normally in the range of 2.5 to 3.0 [30]. The ratio favors both the conversion of methane to carbon monoxide and the carbon monoxide to carbon dioxide as indicated by Equations 3.5.1 and 3.5.3. If the ratio is decreased, the methane concentration increases in the reformed gas, but if the ratio is set at three, the unreacted methane is small. The methane is a diluent in the synthesis reaction given by Equation 3.5.2. 

Increasing the temperature of synthesis results in enhanced crystallinity as would be anticipated because of improved reaction kinetics. However, this observation is also consistent with a crystallization mechanism involving solubility. Furthermore, as the temperature increases so does the equilibrium concentration of lead in solution thus with all else held constant, increased temperature of reaction results in a smaller lattice parameter for the product lead ruthenate pyrochlore. 

A catalyst has no effect on the equilibrium composition. A catalyst increases the rates of both forward and reverse reactions to the same extent. The equilibrium composition and equilibrium concentration do not change when a catalyst is used, but the equilibrium composition is achieved in a shorter time. The role of a solid-phase catalyst in the synthesis of ammonia is shown in Figure 8.13. 

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