Lignocellulosic biomass is addressed as potential sustainable feedstock for green fuels and chemicals. (Hemi)cellulose is the largest constituent of the material. Conversion of these polysaccharides to bio-based platform chemicals is important in green chemical/fuel production and biorefinery. Hydroxymethyl furfural, furfural and levulinic acid are substantial building blocks from (poly)saccharides. Synthesis of these molecules involves acid catalysed hydrolysis/dehydration reactions which leads large formation of insoluble by-products, called humins. Humin obtained from dehydration of glucose is used in this study. Fractionisation of humin was investigated using various solvents (e.g., acetone, H₂O, and NaOH 1%). Characterisation of humin using various techniques including ATR-IR, HR-SEM, solid state NMR, elemental analysis, Raman spectroscopy, pyrolysis, etc. confirms its furan rich structure with aliphatic oxygenate linkages. The influence of thermal treatment on humin was investigated. Humin undergoes a lot of changes both in morphology and structure. Humin loses ca. 45 wt% when preheated to 700 °C (prior to the gasification temperature) and contains above 92 wt% C in mainly aromatic/graphitic structures. Valorisation of humin via dry reforming was studied. Non-catalytic dry reforming of humin is very difficult; however, alkali catalysts (e.g. Na₂CO₃) can enhance the reaction rate tremendously.

The transformation of γ-Al₂O₃ into boehmite (AlO(OH)) under hydrothermal conditions was investigated by in situ Attenuated Total Reflection Infrared (ATR-IR) spectroscopy.

Bio-oil produced from conventional flash pyrolysis has poor quality and requires expensive upgrading before it can be used as a transportation fuel. In this work, a high quality bio-oil has been produced using a novel approach where flash pyrolysis, catalysis and fractionation of pyrolysis vapors using two stage condensation are combined in a single process unit. A bench scale unit of 1 kg/h feedstock capacity is used for catalytic pyrolysis in an entrained down-flow reactor system equipped with two-staged condensation of the pyrolysis vapor. Zeolite-based catalysts are investigated to study the effect of varying acidities of faujasite Y zeolites, zeolite structures (ZSM5), different catalyst to biomass ratios and different catalytic pyrolysis temperatures. Low catalyst/biomass ratios did not show any significant improvements in the bio-oil quality, while high catalyst/biomass ratios showed an effective deoxygenation of the bio-oil. The application of zeolites decreased the organic liquid yield due to the increased production of non-condensables, primarily hydrocarbons. The catalytically produced bio-oil was less viscous and zeolites were effective at cracking heavy molecular weight compounds in the bio-oil. Acidic zeolites, H-Y and H-ZSM5, increased the desirable chemical compounds in the bio-oil such as phenols, furans and hydrocarbon, and reduced the undesired compounds such as acids. On the other hand reducing the acidity of zeolites reduced some of the undesired compounds in the bio-oil such as ketones and aldehydes. The performance of H-Y was superior to that of the rest of zeolites studied: bio-oil of high chemical and calorific value was produced with a high organic liquid yield and low oxygen content. H-ZSM5 was a close competitor to H-Y in performance but with a lower yield of bio-oil. Online fractionation of catalytic pyrolysis vapors was employed by controlling the condenser temperature and proved to be a successful process parameter to tailor the desired bio-oil properties. A high calorific value bio-oil having up to 90% organics was produced using two staged condensation of catalytic pyrolysis vapor. Zeolite-based acidic catalysts can be used for selective deoxygenation, and the catalytic bio-oil quality can be further improved with staged vapor condensation.

Catalytic reforming of biomass derived waste streams in the aqueous phase is a promising process for the production of sustainable hydrogen. Acetic acid will be a major component (up to 20 wt%) in many anticipated gasification feed streams (e.g. the aqueous fraction of pyrolysis oil). Conventional supported (e.g. alumina) catalysts deactivate in the presence of acetic acid rapidly due to coking and metal, support leaching and hence other catalytic systems must be developed to make this process industrially feasible. Carbon nanotubes (CNT) are very resistant to deactivation during acetic acid reforming in supercritical water and are therefore very suitable as catalyst support. Near complete reforming of a 25 wt% acetic acid solution in supercritical water (400 °C, 250 bar) was achieved during 7 h time-on-stream under commercially relevant conditions. The high stability of Ru/CNT for acetic acid reforming in supercritical water has paved the way for studying reforming of real biomass derived waste streams under these conditions.