Abstract
The effect of co-fed hydrogen chloride (HCl) in syngas on the performance of iron and cobalt-based Fischer–Tropsch (FT) catalysts was investigated in our earlier studies (Ma et al. in ACS Catal 5:3124–3136, 2015; Davis et al., DOE final report, 2011; Gnanamani et al. in Catal Lett 144:1127–1133, 2014). For an iron catalyst, lower HCl concentrations (<2.0 ppmw of HCl)) in syngas did not significantly affect the activity, whereas rapid deactivation occurred at higher concentrations (~20 ppmw). With cobalt catalysts, even low concentrations of HCl (100 ppbw) caused catalyst deactivation, and the deactivation rate increased with increasing HCl concentration in the syngas. The deactivation of the catalysts is explained by the chloride being adsorbed on the catalyst surface to (1) block the active sites and/or (2) electronically modify the sites. In this study, XANES spectroscopy was employed to investigate the HCl poisoning mechanism on the iron and cobalt catalysts. Normalized XANES spectra recorded at the Cl K-edge indicate that Cl is indeed present on the catalyst following HCl poisoning and exhibits a structure similar to the family of compounds MCl; two main peaks are formed, with the second peak consisting of a main peak and a higher energy shoulder. At the Co K and Fe K edges, the white line was observed to be slightly increased relative to the same catalyst under clean conditions. There is then the additional possibility that Cl adsorption may act in part to intercept electron density from the FT metallic function (e.g., cobalt or iron carbide). If so, this would result in less back-donation and therefore hinder the scission of molecules such as CO.
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Acknowledgments
This work carried out at the CAER was supported by the Commonwealth of Kentucky and DOE Grant (DE-FC26-08NT0006368). Research described in this paper was performed in part at the Canadian Light Source, which is funded by the Canada Foundation for Innovation, the Natural Sciences and Engineering Research Council of Canada, the National Research Council Canada, the Canadian Institutes of Health Research, the Government of Saskatchewan, Western Economic Diversification Canada, and the University of Saskatchewan.
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Pendyala, V.R.R., Jacobs, G., Ma, W. et al. Fischer–Tropsch Synthesis: XANES Investigation of Hydrogen Chloride Poisoned Iron and Cobalt-Based Catalysts at the K-Edges of Cl, Fe, and Co. Catal Lett 146, 1858–1866 (2016). https://doi.org/10.1007/s10562-016-1820-8
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DOI: https://doi.org/10.1007/s10562-016-1820-8