A high load of inorganics in raw lignocellulosic biomass is known to inhibit the yield of bio-oil and alter the chemical reactions during fast pyrolysis of biomass. In this study, palm kernel shell (PKS), an agricultural residue from palm oil production, and two other woody biomass samples (mahogany (MAH) sawdust and iroko (IRO) sawdust) were pretreated with distilled water or an acidic solution (either acetic, formic, hydrochloric (HCl) or sulfuric acid (H2SO4)) before fast pyrolysis in order to investigate its effect on the primary products and pyrolysis reaction pathways. The raw and pretreated PKS, MAH and IRO were pyrolysed at 600 °C and 5 s with a micro-pyrolyser connected to a gas chromatograph–mass spectrometer/flame ionisation detector (GC-MS/FID). Of the leaching solutions, HCl was the most effective in removing inorganics from the biomass and enhancing the primary pyrolysis product formed compared to the organic acids (acetic and formic acid). The production of levoglucosan was greatly improved for all pretreated biomasses when compared to the original biomass but especially after HCl pretreatment. Additionally, the relative content of the saccharides was maximised after pretreatment with H2SO4, which was due to the increased production of levoglucosenone. The relative content of the saccharides increased by over 70%. This increase may have occurred due to a possible reaction catalysed by the remaining acid in the biomass. The production of furans, especially furfural, was increased for all pretreatments but most noticeable when H2SO4 was used. However, the relative content of acids and ketones was generally reduced for PKS, MAH and IRO across all leaching solutions. The relative content of the phenol-type compound decreased to a large extent during pyrolysis after acid pretreatment, which may be attributed to dehydration and demethoxylation reactions. This study shows that the production of valuable chemicals could be promoted by pretreatment with different acid solutions.

Pyrolysis of biomass to produce liquid fuel and chemicals has been considered as an alternativeto fossil fuel because biomass has a lower environmental impact; moreover, it is renewable andcould be sustainable. However, the process of bio-oil production involves a series of complexchemical reactions which are dependent on the biomass feedstock and composition,temperature, heating rate as well as residence time. In this thesis, pyrolysis was carried out in amicro-pyrolyser connected to a gas chromatograph with a mass spectrometer/flame ionisationdetector to separate and identify the formed volatile compounds.

Firstly, the influence of temperature and residence time on the primary product yield andmechanistic pathways was investigated for the pyrolysis of cellulose, xylan and lignin attemperatures ranging between 400 – 600°C and residence times between 0.5 – 5 s. The resultshowed a general increase in the yield (count/μg sample) for most of the volatile compoundswith increasing temperature and residence time. Additionally, the interaction between theindividual biomass components was investigated. A comparison of the experimental andpredicted results showed that the product yields for some of the volatile compounds wereinhibited, especially for the cellulose-xylan-lignin blend and the native birch wood. This maybe due to the chemical interaction between the biomass and the presence of inorganic materials.The co-pyrolysis of palm kernel shell (PKS), mahogany (MAH) and iroko (IRO) sawdustshowed that the yield of the volatile compounds is dependent on the biomass composition andblend ratio. The co-pyrolysis of PKS, MAH and IRO in equal proportions showed an increasedrelative yield of the sugars compared to the other blend ratios investigated. Finally, the effectof dilute acid pretreatment on PKS, MAH and IRO sawdust prior to fast pyrolysis wasinvestigated. The removal of inorganic materials leads to increased yield, especially the sugarsand the furans. These results are important for understanding the formation mechanism of thepyrolysis products, selection of relevant operating conditions and the selection of a suitablemethodology that could enhance the pyrolysis product yield.

Co-pyrolysis is one possible method to handle different biomass leftovers. The success of the implementation depends on several factors, of which the quality of the produced bio-oil is of the highest importance, together with the throughput and constraints of the feedstock. In this study, the fast co-pyrolysis of palm kernel shell (PKS) and woody biomass was conducted in a micro-pyrolyser connected to a Gas Chromatograph–Mass Spectrometer/Flame Ionisation Detector (GC–MS/FID) at 600 °C and 5 s. Different blend ratios were studied to reveal interactions on the primary products formed from the co-pyrolysis, specifically PKS and two woody biomasses. A comparison of the experimental and predicted yields showed that the co-pyrolysis of the binary blends in equal proportions, PKS with mahogany (MAH) or iroko (IRO) sawdust, resulted in a decrease in the relative yield of the phenols by 19%, while HAA was promoted by 43% for the PKS:IRO-1:1 pyrolysis blend, and the saccharides were strongly inhibited for the PKS:MAH-1:1 pyrolysis blend. However, no difference was observed in the yields for the different groups of compounds when the two woody biomasses (MAH:IRO-1:1) were co-pyrolysed. In contrast to the binary blend, the pyrolysis of the ternary blends showed that the yield of the saccharides was promoted to a large extent, while the acids were inhibited for the PKS:MAH:IRO-1:1:1 pyrolysis blend. However, the relative yield of the saccharides was inhibited to a large extent for the PKS:MAH:IRO-1:2:2 pyrolysis blend, while no major difference was observed in the yields across the different groups of compounds when PKS and the woody biomass were blended in equal amounts and pyrolysed (PKS:MAH:IRO-2:1:1). This study showed evidence of a synergistic interaction when co-pyrolysing different biomasses. It also shows that it is possible to enhance the production of a valuable group of compounds with the right biomass composition and blend ratio. 

Fast pyrolysis is an industrially attractive method to produce fuels and chemicals from biomass; however, to gain better control over the process, the reactions and interactions between the components and decomposition products need elucidation. This study investigated primary reactions during fast pyrolysis of biomass. Pyrolysis of the three main biomass components (cellulose, hemicellulose and lignin) and their blends was carried out with a micro-pyrolyser connected to a Gas Chromatograph-Mass Spectrometer/Flame Ionisation Detector (GC–MS/FID). The blends of the individual components were prepared in similar proportions to that of native biomass (birchwood) and were pyrolysed at 600 °C for 2 s. The results showed that the two-component blends decrease the production of saccharides to a large extent. This was especially noticeable for levoglucosan when cellulose was mixed with either hemicellulose or lignin. Similarly, in the presence of cellulose, the formation of phenolic compounds from lignin was inhibited by 62 %. However, no differences were found in yields of the main products for the xylan-lignin blend compared to those from the individual components. The yields of volatile products from the cellulose-xylan blend were promoted for a majority of the product categories and were most pronounced for the aldehydes. Furthermore, while the formation of the phenols and saccharides was slightly inhibited for the three-component blend, the aldehydes, ketones and furans showed an increased production compared to the weighed sum of products expected, based on the pyrolysis of the individual components. The native biomass showed a similar trend as the three-component blend in all product categories except for the saccharides, which were inhibited to a large extent. This study provides a better understanding of the interactions occurring between different components during fast pyrolysis of biomass.

This study focused on the effect of temperature and residence time on the primary thermal decomposition reactions during a fast pyrolysis of softwood alkali lignin. The use of Py-GC/MS/FID (Micropyrolyser-Gas Chromatography/Mass Spectrometry/Flame Ionization Detector) allowed for rapid heating of the sample and detailed identification and quantification of the pyrolysis products at a temperature range of 400–600 °C, with residence times from 0.5–5 s. The identified primary pyrolysis products were mainly volatile guaiacyl-type compounds. There was a general increase in yield for the majority of the volatile compounds with increased temperature and time. The cleavage of the lignin polymer to linear carbonyl (acetaldehyde) and guaiacyl-type aromatic compounds increased with temperature, while that of catechol and cresol type was mainly favoured at 500 and 600 °C. Based on these results, a mechanistic pathway for the pyrolytic process was proposed, drawing a linkage from structural units of lignin to the formed primary products. In summary, our findings suggest that the primary decomposition reactions that occur under the fast pyrolysis conditions can be controlled by varying the process temperature and residence time, and deliver mechanistic insight into the product distribution from structurally complex lignin material.

The aim of this study was to investigate the effects of temperature and reaction time on the primary pyrolysis of cellulose and xylan. Fast pyrolysis of cellulose and xylan was carried out with a micropyrolyser connected to a gas chromatograph-mass spectrometer/flame ionisation detector (GC–MS/FID) to separate and identify volatile components, both qualitatively and quantitatively. This set-up meant a minimum amount of secondary reactions, low impact of the heating period and at the same time provided rapid and accurate analyses. The two biomass components investigated were: cellulose and hemicellulose (represented by xylan). They were pyrolysed during 0.5, 1, 2 and 5 s (s) and within a temperature range of 400–600 °C. The results showed that levoglucosan (1, 6-anhydro β-D-glucopyranose) is the main chemical compound released during cellulose pyrolysis. It increased with increasing temperature and time. The main volatile compounds produced from pyrolysis of xylan are: 1-hydroxy-2-butanone, 4-hydroxy-5, 6-dihydro-(2 H)-pyran-2-one, 1-hydroxy-2-propanone (acetol), acetaldehyde and hydroxyacetaldehyde (HAA). HAA was the most abundant chemical compound released during xylan pyrolysis, increasing with higher temperatures and time. Acetol and acetaldehyde also showed similar behaviour. The chemical compounds released from cellulose and xylan fast pyrolysis are primary products and assumed to be produced directly from both cellulose and xylan molecules and not from secondary degradation. In this study, possible reaction routes during biomass primary pyrolysis are also suggested based on the product distribution from the thermal decomposition of cellulose and xylan.