Development and recent progress on ammonia synthesis catalysts for Haber–Bosch process

Due to its essential use as a fertilizer, ammonia synthesis from nitrogen and hydrogen is considered to be one of the most important chemical processes of the last 100 years. Since then, an enormous amount of work has been undertaken to investigate and develop effective catalysts for this process. Although the catalytic synthesis of ammonia has been extensively studied in the last century, many new catalysts are still currently being developed to reduce the operating temperature and pressure of the process and to improve the conversion of reactants to ammonia. New catalysts for the Haber–Bosch process are the key to achieving green ammonia production in the foreseeable future. Herein, the history of ammonia synthesis catalyst development is briefly described as well as recent progress in catalyst development with the aim of building an overview of the current state of ammonia synthesis catalysts for the Haber–Bosch process. The new emerging ammonia synthesis catalysts, including electride, hydride, amide, perovskite oxide hydride/oxynitride hydride, nitride, and oxide promoted metals such as Fe, Co, and Ni, are promising alternatives to the conventional fused‐Fe and promoted‐Ru catalysts for existing ammonia synthesis plants and future distributed green ammonia synthesis based on the Haber–Bosch process

Cobalt-lanthanum catalyst precursors for ammonia synthesis: determination of calcination temperature and storage conditions

A thermal decomposition of a cobalt-lanthanum catalyst precursor containing a mixture of cobalt and lanthanum compounds obtained by co-precipitation were studied using thermal analysis coupled with mass spectrometry (TG-MS). Studies revealed that the calcination in air at 500°C is sufficient to transform the obtained cobalt precipitate into Co3 O4 , but it leads to only partial decomposition of lanthanum precipitate. In order to obtain Co/La catalyst precursor containing La2 O3  the calcination in air at the temperature about 800°C is required. However, it is unfavorable from the point of view of textural properties of the catalyst precursor. A strong effect of storage conditions on the phase composition of the studied cobalt-lanthanum catalyst precursor, caused by the formation of lanthanum hydroxide and lanthanum carbonates from La2 O3  when contacting with air, was observed

Properties and activity of the cobalt catalysts for NH₃ &enspsynthesis obtained by co-precipitation – the effect of lanthanum addition

In modern research on catalysts for NH3&enspsynthesis a lot of attention is paid to cobalt. In this work the new catalytic systems based on cobalt are presented. Unsupported cobalt catalysts singly promoted (La or Ba) and doubly promoted (La and Ba) were prepared and tested in NH3&enspsynthesis reaction under commercial synthesis conditions. Characterization studies revealed that lanthanum plays a role of a structural promoter, which improves the surface of catalyst precursors and prevents from sintering during calcination. However, lanthanum has a negative effect on the reduction of cobalt oxide, but the addition of barium promoter (Co/La/Ba catalyst) diminishes the negative impact of La. The co-promotion of cobalt with lanthanum and barium results in the increasing of the active phase surface and improvement of its activity in NH3&enspsynthesis

The genesis of supported cobalt catalysts

The general objectives of this research were to investigate the effect of the support and the gas atmosphere on the decomposition and reduction of cobalt nitrate hexahydrate supported on silica and alumina to gain a greater understanding of the calcination and reduction procedures used in catalyst manufacturing processes. The decomposition was followed by TGA-DSC-MS. The observed breakdown on the unsupported complex is similar but not identical to previous reports with NO detected as an evolved gas. In an oxygen/argon atmosphere the decomposition is generally simplified for the supported samples with a fewer number of weight loss events. When supported on alumina, cobalt nitrate is stabilised with decomposition events shifting to higher temperatures, whereas when supported on silica, cobalt nitrate is destabilised with only one significant decomposition event, which occurs at a lower temperature than that of the unsupported complex. In a hydrogen/nitrogen atmosphere partial decomposition of cobalt nitrate occurs before reduction is initiated with both supported samples. When supported on alumina, cobalt nitrate reduction is catalysed with the two events that occur below 350 °C happening at lower temperatures, while reduction above 350 °C is moved to higher temperatures. The silica-supported complex in contrast exhibits reduction events that are all reduced in temperature relative to the unsupported salt. However, there is evidence of the formation of cobalt silicate with a high temperature reduction. The study has shown that the calcination and direct reduction of supported cobalt nitrate is significantly affected by the support and that different conditions are required to achieve the same state