Fischer-Tropsch synthesis: Effect of solvent on the H2-D2 isotopic exchange rate over an activated nickel catalyst

The effect of solvent on the hydrogen-deuterium isotopic homomolecular exchange rate over a 26.4% Ni/Al2O3 catalyst was investigated using a plug flow reactor at room temperature (23 degrees C) and at atmospheric pressure. In this study, two different molecular weight solvents were tested: n-pentane ((MW) over bar (average molecular weight) = 72), and n-hexadecane ((MW) over bar = 226). At dry (without addition of solvent) and n-pentane solvent addition conditions, similar amounts of H-2 and D-2 are consumed and the concentration of the HD produced is two times the consumption of H-2 or D-2. Thus, these conditions exhibited around 100% exchange with the formation of H-2:HD:D-2 having a 1:2:1 ratio. With n-hexadecane solvent, the initial exchange rate was approximately 45%, but the exchange rate decreased with time and reached a steady state rate after 60 min on-stream. The lower exchange rate of the n-hexadecane solvent might be due to the limited mobility of reactant molecules in the liquid-filled pores of the catalyst. The exchange rate of the catalyst is decreased with increasing molecular weight and density of the solvent. An isotopic partitioning preference was not observed for the nickel catalyst under various co-fed solvents, and similar findings were observed in our previous work (Catalysis Letters 143 (2013)1368-1373). (C) 2016 Elsevier B.V. All rights reserved.