Abstract

The use of alkali promoters has been widely practiced. However, data to compare various promoters is limited for the iron-based catalysts and much of the available data were obtained at low pressure or under a variety of reaction conditions. The importance of the alkali promoter in determining catalytic activity, stability and selectivity merits a comparison of the promoters under suitable reaction conditions. The present study utilizes medium pressure synthesis conditions to compare the alkali promoters under the same reaction conditions and over a wide range of conversion levels. Iron-based Fischer-Tropsch (FT) catalysts undergo a series of phase transformations during activation and use. Activation with carbon monoxide or syngas typically results in the conversion of Fe{sub 2}O{sub 3} to Fe{sub 3}O{sub 4} and ultimately to one or more carbides. During FT synthesis, iron carbides can be oxidized to Fe{sub 3}O{sub 4} if the H{sub 2}O/H{sub 2} or CO{sub 2}/CO ratios are high enough. There has been considerable debate about the active phase of the FT synthesis. Some studies have indicated an active oxide species while most have supported a carbide species. Moessbauer spectroscopy has proven to be an effective technique for the analysis of iron-based FT catalysts. In situ Moessbauer studies have been reported; however, these studies have been performed at low pressure and low conversions. Studies performed at industrially relevant conditions have generally involved removing the catalyst from the reactor followed by passivation which, if not performed properly, will oxidize the catalyst. Herein are reported the Moessbauer results obtained on an unpromoted precipitated iron catalyst that was activated and reacted in a slurry phase, continuous stirred tank reactor at high conversion and under industrially relevant conditions.

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