Numerous species of carbon are observed to be deposited or formed on the surfaces of coked catalysts. The spectrum is broad, ranging from carbides or microcrystalline and amorphous species to highly aromatic/graphitic carbons. Different types of carbon which are of detrimental or beneficial impact on the catalytic activity have been identified and characterized as reviewed in 1 and 2. Mechanisms of coke formation have been studied with respect to the coke precursors as well as growth and termination reactions 3, 4, 5 and 6. The morphology and crystalline order of catalytic carbons have been revealed by means of electron microscopic methods and was discussed from the thermodynamic point of view including the tubular growth on submicron catalytic particles 7 and 8. Details on the high industrial relevance of coking and on the various aspects of catalyst deactivation by coke formation and on the characterization of the different species of carbon which can occur were outlined in a recent issue of Catalysis Today [9], and literature cited therein.
Some of the key parameters that govern the morphology, and thus the adhesion of carbonaceous species to the catalyst surface and the deactivating effect, include
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the presence of other catalytically relevant impurities in coke-forming processes, and
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the content of hydrogen.
In the study reported here, the surface properties and the catalytic activity of a selection of catalyst samples are compared. Furthermore, the structure sensitivity of selected signal parameters in X-ray photoelectron spectrometry (XPS) and secondary-ion mass spectrometry (SIMS) was used to evaluate the sp2/sp3-character and the crystallinity of carbons deposited or generated on the surfaces of various catalysts during operation at high temperature in the BMA process and at low temperature in the vinyl chloride process.
It was suspected that combining SIMS results on hydrogen-related properties of carbon deposits with XPS features previously reported for more or less well-defined grades of carbon (such as graphites, carbon blacks or activated carbons) could also be of some practical use for the characterization of carbon species on the surfaces of these catalysts.
Iron impurities have been observed to have a variety of effects on the carbon morphology and consequently on the catalytic activity.