In Situ Generated Nickel Phosphide Based Catalysts for Hydroprocessing of Levulinic Acid

M. A. Golubeva

doi:10.1134/s0965544121040022

Abstract

This article describes the production of unsupported nickel phosphide\t\t\t\t\tcatalysts generated in situ in а reaction mixture from water-soluble and\t\t\t\t\toil-soluble precursors during the hydroconversion of levulinic acid. These\t\t\t\t\tcatalysts contain crystalline phases, specifically\t\t\t\t\t\tNi12P5 and\t\t\t\t\t\tNi(PO3)2. During the\t\t\t\t\thydrogenation of levulinic acid in toluene in the presence of NiP–TOP, a lower\t\t\t\t\ttemperature and a shorter reaction time contribute to the formation of\t\t\t\t\tγ-valerolactone (100% selectivity). A higher temperature and a longer reaction\t\t\t\t\ttime favor the formation of valeric acid (94% selectivity). In the hydrogenation\t\t\t\t\tof levulinic acid in ethanol in the presence of\t\t\t\t\t\tNiP–H3PO2, the main reaction\t\t\t\t\tproduct is ethyl levulinate (95% selectivity).

Highlights

Biomass is one of the most promising renewable energy sources
The examination confirmed the generation of a crystalline nickel phosphide phase in the NiP–TOP samples prepared at 300–350°C in toluene after 6 h of the reaction (Fig. 1a) and in the NiP–H3PO2 samples prepared at 250–350°C in ethanol after 6 h of the reaction (Fig. 1b)
The catalytic activity of the NiP–TOP and NiP–H3PO2 nickel phosphides generated in situ was examined in the hydrogenation of levulinic acid

Summary

Introduction

Biomass is one of the most promising renewable energy sources. The main components of lignocellulosic biomass are lignin, cellulose, and hemicellulose. References [16,17,18] suggest a method for the hydrodeoxygenation of oxygen-containing compounds in the presence of transition metal phosphides, which involves in situ generation of an unsupported phosphide active phase directly in the hydrodeoxygenation reactor. This method has been well known to be employed for hydroconversion of heavy oil residues in the presence of transition metal sulfides, which can be generated in situ from oxides due to H2S formation in the reaction mixture [19]

Objectives

Results

Conclusion