Abstract

Hydrodeoxygenation (HDO) activity of a typical hydrotreating catalyst, sulfided NiMo/γ-Al2O3 for deoxygenation of a fatty acid has been explored in a batch reactor at 54 bar and 320 °C in the presence of contaminants, like phospholipids, which are known to be present in renewable feeds. Oleic acid was used for the investigation. Freshly sulfided catalyst showed a high degree of deoxygenation activity; products were predominantly composed of alkanes (C17 and C18). Experiments with a major phospholipid showed that activity for C17 was greatly reduced while activity to C18 was not altered significantly in the studied conditions. Characterization of the spent catalyst revealed the formation of aluminum phosphate (AlPO4), which affects the active phase dispersion, blocks the active sites, and causes pore blockage. In addition, choline, formed from the decomposition of phospholipid, partially contributes to the observed deactivation. Furthermore, a direct correlation was observed in the accumulation of coke on the catalyst and the amount of phospholipid introduced in the feed. We therefore propose that the reason for the increased deactivation is due to the dual effects of an irreversible change in phase to aluminum phosphate and the formation of choline.

Highlights

  • Fossil fuel depletion, caused by increasing demands and finite resources, as well as concern about greenhouse gas (GHG) emissions, has led to a search for alternative renewable sources of energy [1,2]

  • NiMo/γ-Al2 O3 catalyst has been examined for HDO of oleic acid in the presence of a major bio/algal oil phospholipid, phosphatidylcholine

  • We propose that the observed deactivation is due to formation of both phosphoric acid and choline from the decomposition of the phosphatidylcholine

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Summary

Introduction

Fossil fuel depletion, caused by increasing demands and finite resources, as well as concern about greenhouse gas (GHG) emissions, has led to a search for alternative renewable sources of energy [1,2]. The type of biomass employed can be of different kinds, but mainly: carbohydrates, lignocellulosic material, and waste animal fats or waste/non-edible oils have been considered [3]. All of these renewable resources are suitable for upgrading to liquid biofuel in many different processes, for example, to bio-ethanol by fermentation of sugar or starch, to bio-diesel by transesterification of fat/oil, and to renewable diesel through catalytic hydrodeoxygenation of triglycerides and fatty acids [4,5]. Animal fats and non-edible oils are composed of triglycerides, with high amounts of oxygen They can contain minor, but varying, amounts of free fatty acids, phospholipids, sterols, pigments, and waxes. The challenge for bio-oil upgrading depends on its viability, properties, composition, competition with the food grade biomass, and presence of impurities

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