Valorisation of unconventional lignocellulosic biomass into bioenergy and bioproducts using ionic-liquid based technologies
Creators: name: Hennequin, Louis Henri Marius
Publisher: name: Imperial College London
Year: 2022

description: In order to transition energy use away from fossil fuels, the transformation of renewable lignocellulosic biomass needs to be improved and its supply of sustainable bioenergy into a wider bioeconomy increased. Achieving this will require: (1) renewable, cheap and high-quality lignocellulosic feedstocks, (2) a robust process to transform this feedstock into bioenergy and finally (3) a system to recover and use this bioenergy as well as value-added products. In this PhD, multiple examples were used to explore unconventional feedstocks, novel transformation processes and opportunities for value-added products. Feedstocks ranging from invasive species threatening the UK environment, Rhododendron and Japanese Knotweed (Chapter 3), metal contaminated waste wood (Chapter 4), metal enriched biomass grown on marginal land (Chapter 5), and wastewater irrigated willow, a leading dedicated bioenergy crop (Chapter 6). While conventional bioenergy systems often burn wood pellets for energy co-generation, the innovative transformation process of ionic liquid-based technologies are explored as flexible enough to fractionate unconventional biomass feedstocks and deliver high yields of sustainable bioenergy and bioproducts. This was allowed by the unique and tuneable properties of protic ionic liquids. Here dimethylbutyl-hydrogen sulphate - [DMBA][HSO4], a cheap hydrogen sulphate [HSO4]- based ionic liquid, and 1-methylimidazolium chloride - [C1Him][Cl], were used in the ionic-liquid based ionoSolv process. Key efficiency parameters such as temperature, reaction time, biomass to solvent loading and solvent recycling, were explored. The process was also challenged with the presence of diverse metal contamination to determine the potential to extract the metals and produce a fermentable pulp and lignin in parallel. Bioenergy recovery from the ionoSolv process was explored as well as the potential to recover multiple value-added products. In addition to determination of heating values of isolated lignin as well as hydrolysis and fermentation yields of cellulose rich pulps into bioethanol, interactions of contaminating metals and their impact on yeast fermentation yields were investigated. This investigation highlights the benefits of [C1Him][Cl] ionic liquid pretreatment for the production of clean bioenergy and bioproducts from highly contaminated feedstocks. As an important property of ionic liquids is that they can act as media for electrochemical reactions, electrodeposition of metals from ionic liquid liquor, metal extraction efficiencies and any detrimental interactions with ionic liquid recycling were assessed. To further diversify system outputs beyond bioenergy alone, production of bio-oils, char and gases from pyrolysis of post-hydrolysis residue was determined, as well as the possibility for recovery of phytochemicals as potential complementary value-added products. This research highlights that unconventional feedstocks have the potential to support a developing bioeconomy and that the reallocation of waste and reclamation of contaminated soils and waters could act as a financial, social and environmental levers to improve the sustainability of bioenergy production. The studies also showcase how a versatile engineered ionic-liquid pretreatment has the potential to transform environmental burdens into resources that are compatible with the diversification of multiple product streams. Taken together, these findings can serve as a proof-of-concept for integrated scale-up of sustainable ionic-liquid based biorefinery.