Water-wax behaviour in porous silica at low temperature Fischer-Tropsch conditions

• Published in: Applied catalysis. A, General Vol. 572; pp. 142 - 150
• Main Authors: Zheng, Qingyuan, Brown, Jacob L., Mantle, Mick D., Sederman, Andrew J., Baart, Timothy A., Guédon, Constant M., Gladden, Lynn F.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 25-02-2019
• Subjects: Fischer-Tropsch synthesis; NMR; Phase behaviour; Porous media; Water; Water; Porous media; Fischer-Tropsch synthesis; NMR; Phase behaviour
• ISSN: 0926-860X; 1873-3875
• DOI: 10.1016/j.apcata.2018.11.022

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•Operando magnetic resonance measurements of water-wax behaviour in porous silica pellets.•Reactor operated at 195 °C with water pressure in the range 3–13.6 bar.•Capillary-condensation of water occurs within the initially wax-saturated pore space.•Evidence that water displaces wax from the initially wax-saturated pore space.•As much as 40% of the pore surface is estimated to be covered by water at the highest water pressures studied.
Water is a major product of Fischer-Tropsch synthesis, and hence the behaviour of water within Fischer-Tropsch synthesis catalysts and its potential influence on catalyst rate and selectivity are questions of long-standing interest. The present work applies three different magnetic resonance techniques to study how water interacts with a model wax, n-octacosane, within the pore space of a porous silica of mean pore size ∼18 nm. 1H magnetic resonance spectroscopy, spin-lattice relaxation time and pulsed-field gradient measurements were performed at 195 °C, and for water pressure in the range 3–13.6 bar, conditions relevant to low temperature Fischer-Tropsch synthesis. The uptake of water within this system is shown to be very similar to that observed for capillary condensation of water within the empty pore space of the same porous silica under the same experimental conditions; suggesting that capillary condensation of water within the wax-saturated pores is occurring. The behaviour of water is characterised by two regimes. At low water relative pressures of ∼0.3 ≤ P/P0 ≤ ∼0.8 water moves into the pore space, displacing wax from the pore surface and existing as a water-rich layer between the pore surface and an oil-rich phase in the centre of the pore; the strong interaction with the pore surface is evidenced by the short nuclear spin relaxation time values of water at the lowest pressures which then increase slightly as multi-layer adsorption at the pore surface occurs with increase in pressure. In the water relative pressure range ∼0.8 ≤ P/P0 ≤ ∼0.97, condensation of water within the pores is observed, characterised by increases in both spin-lattice relaxation time and molecular diffusivity. Analysis of the data suggests that as much as ∼40% of the pore surface is occupied by condensed water after condensation has occurred. It is suggested that these two regimes of water behaviour inside initially wax-filled pores might explain previously reported aspects of the behaviour of Fischer-Tropsch catalyst performance as a function of pore size and amount of co-fed water.