Ammonia synthesis promoted

Lanthanides as modifiers to other oxides in aluminas In zirconias In iron oxide Lanthanide oxides in mixed oxides With aluminas With iron oxides With other transition metal oxides To maintain surface area To increase oxidation rates To increase methanation rates For conduction in electrocatalysis For ammonia synthesis promotion To provide sulfur oxides (SO.,) control For dehydrogenation in carbon monoxide reactions For oxidation... 

It has been claimed that carbon-supported ruthenium-based catalysts for ammonia synthesis show some important drawbacks, such as high catalyst cost and methanation of the carbon snpport under industrial reaction conditions. This has stimnlated the research for alternative catalysts, although the use of carbon snpports is a common feature. One example of these new catalysts is provided by the work of Hagen et al. [61], who reported very high levels of activity with barinm-promoted cobalt catalysts snpported on Vulcan XC-72. It was demonstrated that althongh cobalt had received little attention as a catalyst for ammonia synthesis, promotion with barium and the nse of a carbon support resulted in very active catalysts with very low NH3 inhibition. 

M. Temkin and V. Pyzhev. Kinetics of ammonia synthesis, promoted iron catalysts. Acta Physicochimica U.R.S.S., l2 3) 327-356, 1940. 

K.S. Rama Rao et al [8] lately described new type of carbon coated AljO, support for the preparation of Ru/C-Al Oj catalyst for ammonia synthesis promoted by impregnation with CsNO,. Above used carbon-coated aluminium oxides, were prepared by pyrolysis of an alkene on AljOj. 

Recent commercialization efforts have focused on improved activity synthesis catalysts, which allow ammonia synthesis to be conducted at significantly lower pressures and temperatures. Catalyst manufacturers have focused on enhancing the activity of the iron-based catalyst through the use of promoters (23). 

Promoters. Many industrial catalysts contain promoters, commonly chemical promoters. A chemical promoter is used in a small amount and influences the surface chemistry. Alkali metals are often used as chemical promoters, for example, in ammonia synthesis catalysts, ethylene oxide catalysts, and Fischer-Tropsch catalysts (55). They may be used in as Httie as parts per million quantities. The mechanisms of their action are usually not well understood. In contrast, seldom-used textural promoters, also called stmctural promoters, are used in massive amounts and affect the physical properties of the catalyst. These are used in ammonia synthesis catalysts. 

The industrial catalysts for ammonia synthesis consist of far more than the catalyticaHy active iron (74). There are textural promoters, alumina and calcium oxide, that minimise sintering of the iron and a chemical promoter, potassium (about 1 wt % of the catalyst), and possibly present as K2O the potassium is beheved to be present on the iron surface and to donate electrons to the iron, increasing its activity for the dissociative adsorption of N2. The primary iron particles are about 30 nm in size, and the surface area is about 15 m /g. These catalysts last for years. 

Remaining trace quantities of CO (which would poison the iron catalyst during ammonia synthesis) are converted back to CH4 by passing the damp gas from the scmbbers over a Ni methanation catalyst at 325° CO -t- 3H2, CRt -t- H2O. This reaction is the reverse of that occurring in the primary steam reformer. The synthesis gas now emerging has the approximate composition H2 74.3%, N2 24.7%, CH4 0.8%, Ar 0.3%, CO 1 -2ppm. It is compressed in three stages from 25 atm to 200 atm and then passed over a promoted iron catalyst at 380-450°C ... 

Promotion We use the term promotion, or classical promotion, to denote the action of one or more substances, the promoter or promoters, which when added in relatively small quantities to a catalyst, improves the activity, selectivity or useful lifetime of the catalyst. In general a promoter may either augment a desired reaction or suppress an undesired one. For example, K or K2O is a promoter of Fe for the synthesis of ammonia. A promoter is not, in general, consumed during a catalytic reaction. If it does get consumed, however, as is often the case in electrochemical promotion utilizing O2 conducting solid electrolytes, then we will refer to this substance as a sacrificial promoter. 

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). 

The effect of alkali additives on N2 chemisorption has important implications for ammonia synthesis on iron, where alkali promoters (in the form of K or K20) are used in order to increase the activity of the iron catalyst. 

C.G. Yiokari, G.E. Pitselis, D.G. Polydoros, A.D. Katsaounis, and C.G. Vayenas, High pressure electrochemical promotion of ammonia synthesis over an industrial iron catalyst, /. Phys. Chem. 104, 10600-10602 (2000). 

Figure 9.33. Ammonia synthesis rate and current response to a step change in the catalyst potential Uwr of the promoted Fe/CaZro9lno, Oj.u catalyst,43 Reprinted with permission from the American Chemical Society.

Proton conductors ammonia synthesis, 468 conductivity, 93 ethylene oxidation, 470 hydrogen oxidation, 457 list of electrochemically promoted reactions, 146... 

What is the rate-determining step of the ammonia synthesis reaction Describe the function of promoters in the ammonia synthesis catalyst. 

Ammonia synthesis N2 + h2 Iron promoted with A1203 and K nh3... 

While chlorine is a poison for the ammonia synthesis over iron, it serves as a promoter in the epoxidation of ethylene over silver catalysts, where it increases the selectivity to ethylene oxide at the cost of the undesired total combustion to C02. In this case an interesting correlation was observed between the AgCl27Cl ratio from SIMS, which reflects the extent to which silver is chlorinated, and the selectivity towards ethylene oxide [16]. In both examples, the molecular clusters reveal which elements are in contact in the surface region of the catalyst. 

Potassium is a well-known promoter in the ammonia synthesis and the Fischer-Tropsch synthesis, where it is thought to assist the dissociation of the reactants,... 

N2 and CO, respectively [31,32], Empirical knowledge about the promoting effect of many elements has been available since the development of the iron ammonia synthesis catalyst, for which some 8000 different catalyst formulations were tested. Recent research in surface science and theoretical chemistry has led to a fairly complete understanding of how a promoter works [33,34],... 

Catalysts consisting of more than one component are often superior to monometallic samples. Model studies with potassium on Fe surfaces revealed, for example, the role of the electronic promoter in ammonia synthesis. A particularly remarkable case was recently reported for a surface alloy formed by Au on a Ni(lll) surface where the combination of STM... 

In February 1909, the results of the experiments on nitride formation had led to the outline of a patent application which covered the preparation of metal nitrides in the presence of auxiliary substances. Following a hypothetical concept of the action of these additions, they were defined as flux promoters." This draft of an application ended with the following sentence Finally, it is also advantageous to add a flux promoter to metals or alloys which serve as catalysts for the ammonia synthesis. This statement was made in view of the early catalytic experiments in which we had observed the synthesis of traces of ammonia in the presence of catalysts similar to those which acted favorably for the nitride formations. 

Metals other than iron which catalyze the ammonia synthesis such as osmium, ruthenium, uranium, and molybdenum can also be promoted by added substances. However, several of these metals do not show improvements of the same magnitude as does iron. Further-... 

Recently, independent publications by Kojima and Aika and workers from Topsoe have reported on the high activity and stability of Cs/ C03M03N based catalysts for ammonia synthesis. The activity has been found to be significantly higher than for the commercial iron based catalyst. Table 3 gives a comparison of the ammonia synthesis rates of Cs and K promoted catalysts at various promoter loadings (2, 5, 10 and 30 mol%) for low conversion at 400°C and atmospheric pressure. ... 

The above are equilibrium reactions, and their successful exploitation requires that they be carried out under conditions in which the equilibrium favors the product. Specifically, this requires that the adsorbed species in Reactions (D)-(I) not be held so tightly on the catalyst surfaces as to inhibit the reaction. On the other hand, strong interaction between adsorbate and catalyst is important to break the bonds in the reactant species. Optimization involves finding a compromise between scission and residence time on the surface. Although we are especially interested in metal surfaces, those constituents known as promoters in catalyst mixtures are also important. It is known, for example, that the potassium in the catalyst used for the ammonia synthesis shifts Equilibrium (F) to the right and also increases the rate of Reaction (D) by lowering its activation energy from 12.5 kJ mole to about zero. 

A complex nanostructured catalyst for ammonia synthesis consists of ruthenium nanoclusters dispersed on a boron nitride support (Ru/BN) with barium added as a promoter (33). It was observed that the introduction of barium promoters results in an increase of the catalytic activity by 2—3 orders of magnitude. The multi-phase catalyst was first investigated by means of conventional HRTEM, but this technique did not succeed in identifying a barium-rich phase (34). It was even difficult to determine how the catalyst could be active, because the ruthenium clusters were encapsulated by layers of the boron nitride support. By HRTEM imaging of the catalyst during exposure to ammonia synthesis conditions, it was found that the... 

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