Fischer–Tropsch Synthesis: Effect of K Loading on the Water–Gas Shift Reaction and Liquid Hydrocarbon Formation Rate over Precipitated Iron Catalysts
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The effect of K loading on the water–gas shift (WGS) reaction and hydrocarbon formation rate during Fischer–Tropsch synthesis (FTS) was studied over 100 Fe/5.1 Si/2 Cu/x K (x = 1.25 or 3) precipitated catalysts using a 1-L continuously stirred tank reactor. The catalysts were tested over a wide range of experimental conditions: 260–270 °C, 1.3 MPa, H2/CO = 0.67 and 20–90 % CO conversions. On the low K loading (1.25 % K) Fe catalyst, the H2 deficiency required for the FTS reaction was made up by the WGS reaction only at high CO conversion level, i.e. >70 %; however, increasing potassium loading to 3 % dramatically improved the WGS reaction rate which provided enough hydrogen for the FTS reaction even at low CO conversion level, i.e. 30 %. Kinetic analysis suggests that increasing K loading resulted in significant increases in the WGS rate constant relative to that of FTS, which is a major cause of the high WGS activity on the high K loading catalyst. Both the low and high potassium containing iron catalysts have high liquid oil and solid wax formation rates, i.e. 0.78–0.93 g/g-cat/h at 260 °C, 1.3 MPa, H2/CO = 0.67 and 50 % CO conversion, but increasing potassium loading from 1.25 to 3 % shifted the primary product to wax (70 %) from oil (73.5 %). The wax fraction increased with increasing CO conversion for both iron catalysts. The effect of K loading on initial FTS activity and hydrocarbon distribution/selectivity of the Fe catalysts was also studied. High K loading, i.e. 3 % K, increased the iron carburization rate and significantly shortened the induction period of the FTS reaction. Secondary reactions of olefins were remarkably suppressed and the olefin content was greatly enhanced with increasing K loading from 1.25 to 3 %, consistent with a number of studies in the open literature.
KeywordsFischer–Tropsch synthesis Water–gas shift Fe based catalyst Potassium promoter Carburization Reaction rate constant Hydrocarbon productivity
This work was made possible by financial support from DOE grants (DE-AC22-99FT40540) and the Commonwealth of Kentucky.
- 1.Davis BH (1993, 1999, 2002, 2011) DOE final technical reportsGoogle Scholar
- 2.Bukur DB (1994, 1999, 2003) DOE final reportsGoogle Scholar
- 3.Huffman GP (2001, 2002, 2005) DOE final reportsGoogle Scholar
- 19.Kolbel H (1960) Kalium als Strucktureller und Energetischer Promotor in isenkatalysatoren In: Actes du Deuxieme Congres Znternational de Catalyse. Technip: Paris, vol 11, pp 2075–2099Google Scholar
- 20.Kolbel H, Giehring H (1963) Brennstojj Chem 44:343Google Scholar
- 22.Jacobs G, Sarkar A, Davis H, Cronauer D, Kropf AJ, Marshall CL (2009) In Advances in Fischer–Tropsch synthesis, catalysts, and catalysis, p 119Google Scholar
- 23.Ribeiro MC, Jacobs G, Davis BH, Cronauer DC, Kropf AJ, Marshall CL (2010) J Phys Chem 114:7895Google Scholar
- 27.Anderson RB (1984) The Fischer–Tropsch synthesis. Wiley, New York, pp 140–159Google Scholar
- 28.Yao Y (2011) Fischer–Tropsch synthesis using CO2 containing syngas mixtures over cobalt and iron based catalysts. PhD thesis, JohannesburgGoogle Scholar