Haber ammonia synthesis catalyst

Around 1900 Fritz Haber began to investigate the ammonia equilibrium [11] at atmospheric pressure and found minimal ammonia concentrations at around 1000 °C (0.012 %). Apart from Haber, Ostwald and Nernst were also closely involved in the ammonia synthesis problem, but a series of mistakes and misunderstandings occurred during the research. For example, Ostwald withdrew a patent application for an iron ammonia synthesis catalyst because of an erroneous experiment, while Nernst concluded that commercial ammonia synthesis was not feasible in view of the low conversion he found when he first measured the equilibrium at 50 - 70 bar [12] - [14],... 

If this is done enough times, fairly pure hydrogen can be generated for use in Haber ammonia synthesis. The carbon monoxide and hydrogen can also be converted to methanol, an alcohol that can be burned as a fuel, or, if repeated many times and with a catalyst, converted into the long-chain carbon compounds that make up waxes and oils. 

Ammonia has been produced commercially from its component elements since 1909, when Fritz Haber first demonstrated the viability of this process. Bosch, Mittasch and co-workers discovered an excellent promoted Fe catalyst in 1909 that was composed of iron with aluminium oxide, calcium oxide and potassium oxide as promoters. Surprisingly, modem ammonia synthesis catalysts are nearly identical to that first promoted iron catalyst. The reaction is somewhat exothermic and is favoured at high pressures and low temperatures, although, to keep reaction rates high, moderate temperatures are generally used. Typical industrial reaction conditions for ammonia synthesis are 650-750 K and 150-300 atm. Given the technological importance of the... 

The exact role of promoters is not very well understood in many cases, but it is now generally accepted that it is related to the formation of specific electronic surface states necessary for the given catalytic reaction. It apparently does not matter how that electronic state is produced that is, whether it is formed in the preparation of the native catalyst surface or by the presence of some other component which induces the necessary state. As an example, the presence of small amounts of aluminum and potassium oxides on iron-iron oxide catalyst in the Haber ammonia synthesis greatly improves its activity. Either promoter alone has no significant effect on the process. Why Such questions remain as fodder for further industrial or graduate research. 

Alwin Mittasch joined BASF in 1904 as a co-worker of Carl Bosch and started the search for suitable ammonia synthesis catalysts soon afterward. These efforts were considerably intensified after Haber s successful experiments but, at first, only with limited success. He mentioned (4) In particular iron failed, despite wide variations of the preparation conditions and admixtures. The breakthrough was obtained by accident A sample of Swedish magnetite left over from other experiments was investigated on November 6, 1909, by Mittasch s collaborator Dr. Wolf and exhibited remarkably high ammonia yields. The decisive patent application of January 9, 1910, says the following ... 

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. 

Silvery, shiny, and hard. Unique metal, gives off an odor as it forms volatile 0s04 on the surface (oxidation states 81). Osmium is the densest element (22.6 g cm3 record ). Was replaced in filaments (Osram) by the cheaper tungsten. Used in platinum alloys and as a catalyst. Haber s first catalyst in ammonia synthesis was osmium, which fortunately could be replaced by doped iron. The addition of as little as 1 to 2 % of this expensive metal increases the strength of steel (e.g. fountain-pen tips, early gramophone needles, syringe needles). 

Since 1923, methanol has been made commercially from synthesis gas, the route that provides most of the methanol today. The plants are oEten found adjacent to or integrated with ammonia plants for several reasons. The technologies and hardware are similar, and the methanol plant can use the CO2 made in the Haber ammonia process. In this case, the route to methanol is to react the CO2 with methane and steam over a nickel catalyst to give additional CO and H2 and then proceed to combine these to make methanol ... 

The reasoning which led the author to make this first shot in the dark regarding the usefulness of combinations of solid compounds as ammonia catalysts was as follows If we assume that a labile iron nitride is an interminate in the catalytic ammonia synthesis, every addition to the iron which favors the formation of the iron nitride ought to be of advantage. In other words, the hypothesis was used that surface catalysis acts via the formation of intermediate compounds between the catalyst and one or more of the reactants. An experimental support for this theory was the fact that a stepwise synthesis via the formation and successive hydrogen reduction of nitrides had been carried out with calcium nitrides (Haber), and cerium nitrides (Lipski). Later, the author found molybdenum nitride as being the best intermediate for such a stepwise synthesis. 

To conclude, it is worth recording the advice given to the author at the very start of his career by the veteran catalytic chemist Alwin Mittasch, who had been Fritz Haber s officer in charge of catalyst research for the ammonia synthesis In all catalytic studies only the very purest is good enough . 

Reactions which may occur on sites consisting of one or two atoms only on the surface of the catalyst are generally known as facile reactions. Reactions involving hydrogenation on metals are an example. Eor such reactions, the state of dispersion or preparation methods do not greatly affect the specific activity of a catalyst. In contrast, reactions in which some crystal faces are much more active than others are called structure sensitive. An example is ammonia synthesis (discovered by Fritz Haber in 1909 (Moeller 1952)) over Fe catalysts where (111) Fe surface is found to be more active than others (Boudart 1981). Structure-sensitive reactions thus require sites with special crystal structure features, which... 

Researchers returned to the oxidation of ammonia in air, (recorded as early as 1798) in an effort to improve production economics. In 1901 Wilhelm Ostwald had first achieved the catalytic oxidation of ammonia over a platinum catalyst. The gaseous nitrogen oxides produced could be easily cooled and dissolved in water to produce a solution of nitric acid. This achievement began the search for an economic process route. By 1908 the first commercial facility for production of nitric acid, using this new catalytic oxidation process, was commissioned near Bochum in Germany. The Haber-Bosch ammonia synthesis process came into operation in 1913, leading to the continued development and assured future of the ammonia oxidation process for the production of nitric acid. 

Table 5.1 shows an application of XPS to the study of the promoted iron catalyst used in the Haber synthesis of ammonia. The sizes of the various electron intensity peaks allows a modest level of quantitative analysis. This catalyst is prepared by sintering an iron oxide, such as magnetite (Fe304) with small amounts of potassium nitrate, calcium carbonate, aluminium oxide and other trace elements at about 1900 K. The unreduced solid produced on cooling is a mixture of oxides. On exposure to the nitrogen-hydrogen reactant gas mixture in the Haber process, the catalyst is converted to its operative, reduced form containing metallic iron. As shown in Table 5.1, the elemental components of the catalyst exhibit surface enrichment or depletion, and the extent of this differs between unreduced and reduced forms. 

In most processes the reaction takes place on an iron catalyst. The reaction pressure is normally in the range of 150 to 250 bar, and temperatures are in the range of 350°C to 550°C. At the usual commercial converter operating conditions, the conversion achieved per pass is only 20% to 30%53. In most commercial ammonia plants, the Haber recycle loop process is still used to give substantially complete conversion of the synthesis gas. In the Haber process the ammonia is separated from the recycle gas by cooling and condensation. Next the unconverted synthesis gas is supplemented with fresh makeup gas, and returned as feed to the ammonia synthesis converter74. 

In 1905 Haber reported a successful experiment in which he succeeded in producing NH3 catalytically. However, under the conditions he used (1293 K) he only found minor amounts of NH3. He extrapolated his value to lower temperatures (at 1 bar) and concluded that a temperature of 520 K was the maximum temperature for a commercial process. This was the first application of chemical thermodynamics to catalysis, and precise thermodynamic data were not then known. At that time Haber regarded the development of a commercial process for ammonia synthesis as hopeless and he stopped his work. Meanwhile, Nernst had also investigated the ammonia synthesis reaction and concluded that the thermodynamic data Haber used were not correct. He arrived at different values and this led Haber to continue his work at higher pressures. Haber tried many catalysts and found that a particular sample of osmium was the most active one. This osmium was a very fine amorphous powder. He approached BASF and they decided to start a large program in which Bosch also became involved. 

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