Biomass wastes are sustainable, renewable, and promising energy sources. In this study, the pyrolysis of agricultural biomass was investigated to determine the most promising process parameters for pyrolytic gas production. The pyrolysis investigations were carried out under nitrogen atmosphere at 300, 400, 500, and 600 ?C on the microscale using simultaneous thermal analysis and a laboratory-scale semi-batch vertical reactor. The solid, liquid, and gaseous products were characterised in detail, including the elemental and chemical composition. The gas and liquid products analyses were provided. It was found that the quality of the pyrolytic gas increased with temperature, both in terms of the pyrolytic gas yield and concentration of gaseous components (hydrogen and methane), whereas the carbon dioxide concentration decreased with temperature. The condensed vapours were rich in phenolic and aromatic compounds, and it was noted that the acetic acid concentration increased with temperature. The chemical functional groups in the char were determined using infrared spectroscopy. The carbon content increased with temperature, whereas the hydrogen content decreased. Further decomposition of the organic matrix was observed with increasing temperature. Additionally, chemical modelling of pyrolytic gas was performed using Ansys Chemkin-Pro software and compared with the experimental results. The computational results showed a good correlation with the measured pyrolytic gas composition, especially in the case of the major gas components.

This study focuses on chemical recycling of plastics from waste electrical and electronic equipment (WEEE), which constitutes a problematic waste fraction due to the presence of brominated flame retardants. An auger reactor has been designed and used for this study. Real WEEE material provided by Stena Technoworld has been pyrolyzed under different temperature conditions. The performance of the reactor as well as other important parameters such as the fate of the bromine have been investigated and evaluated. The main outcome of this investigation is to simulate a continuous process, which can be useful for designing a full-scale industrial process. The mass balance results after performing thermal treatment at 400, 500, and 600 °C, showed a high gas yield (44 %wt) at the temperature of 600 °C, which energy content is enough to self-sustain the auger reactor. At the low temperature of 400 °C the oil production reaches its maximum yield as well as maximum concentration of bromine, corresponding to 0.5 wt% in the oil. Several valuable organic compounds have been detected in the oil composition, which can be used as precursors for feedstock recycling producing new plastics.

Consumption of electronics increases due to modern society’s growing needs, which leads to increasing generation of waste electrical and electronic equipment (WEEE). Recycling of WEEE has been a global concern during the last few decades because of the toxic compounds that are produced during recycling. Different recycling techniques have been adapted on a commercial scale in order to overcome this issue, but the recycling of WEEE still lacks the technology to treat different kinds of feedstocks and to maximise the recycling rates. Pyrolysis is an alternative that has not been commercialised yet. One of the challenges for the implementation of this technology is the toxic brominated organic compounds that can be found in the pyrolysis oils.

In this study, tetrabromobisphenol A (TBBPA), one of the major flame retardants, is reduced in three different WEEE fractions through solvent extraction as a treatment prior to pyrolysis. Two solvents have been experimentally investigated: isopropanol and toluene, the latter of which can be derived from pyrolysis oil. The results indicate that TBBPA was extracted during pre-treatment. Moreover, the total bromine content of WEEE material was reduced after the treatment with a maximum reduction of 36.5%. The pyrolysis experiments indicate that reduction of several brominated organic compounds was achieved in almost all the tested cases, and two brominated compounds (2,4,6-tribromophenol and 2,5-Dibromobenzo(b)thiophene) reached complete removal. Also, the thermal decomposition behaviour of the raw samples and the treated was investigated, showing that the reduction of TBBPA influences the decomposition by shifting the starting decomposition temperature.

Waste electric and electronic equipment (WEEE) has been a cause of concern in the past decades due to their complex composition, their low recycling rates, and, of course, their increasing volumes. This chapter summarizes the main challenges that have to be faced and the opportunities relying on the proper management of this waste fraction. The current legislations existing globally are stated together with goals for recycling on the different subcategories of WEEE. Then the composition is analyzed for evaluating the potential improvement of the current systems. Finally, a deep literary review on the existing technologies as well as trends of research during the past years is also presented. 

Sulfonated Kraft lignin, the most available commercial lignin of today, has high sulfur content due to the extraction and the subsequent sulfonation processes. In this work, the evolution of sulfur during fast pyrolysis of sulfonated Kraft lignin has been studied. Fast Pyrolysis experiments have been done using Py-GC/MS. It is found that main sulfur-containing products in the pyrolytic vapors are present as the following small molecular compounds: H2S, SO2, CH3SH, CH3SCH3, and CH3SSCH3. This indicates that sulfur-containing radicals preferentially combine with the other small radicals such as  H and  CH3 during fast pyrolysis process. Sulfur is suggested to be mainly present as sulfite ( SO−3) and sulfide ( S ) in the sulfonated Kraft lignin. Sulfite that is incorporated into lignin during the sulfonation process mainly result in the formation of SO2. The nature of the sulfur links created during the Kraft pulping process is difficult to determine, but they are supposed to mainly exist in form of sulfide ( S ) bonds, which lead to the formation of H2S, CH3SH, CH3SCH3 and CH3SSCH3.

The thermal properties of cellulose, hemicellulose and lignin can be utilized to improve the characteristics of pyrolysis liquids. In this study, a concept of stepwise pyrolysis to fractionate the liquid based on the thermal properties of the biomass constituents was investigated. Lignocellulosic biomass was thermally treated in two steps: 200–300 °C followed by 550 °C. Derived liquids were studied for GC/MS analysis, water content, acid concentration and a solvent extraction method. Pyrolytic liquid derived from 550 °C after treatment at lower temperatures have a higher relative composition of phenolic compounds compared to one-step pyrolysis (increased from 58 to 90% of GC/MS peak area). Also, compounds known to promote aging, such as acids and carbonyl compounds, are derived at lower temperatures which may suppress aging in the liquid derived downstream at 550 °C. For liquids derived at 550 °C, the total acid number was reduced from 125 in one-step treatment to 14 in two-step treatment. Overall, no significant difference in the total liquid yield (sum of the liquids derived in separated treatments) nor any variations in their collective composition compared to one-step treatment at 550 °C was observed, i.e. stepwise pyrolysis can be utilized for direct fractionation of pyrolytic vapors.

The automotive shredder residue (ASR) or shredder light fraction (SLF) is the remaining fraction from the metal recovery of end-of-life vehicles (ELVs). While processes for metal recovery from ELVs are well developed, the similar process for ASR remains a challenge. In this work, low-temperature pyrolysis of the ASR fraction was investigated under the assumption that a low temperature and inert environment would enhance the metal recovery, i.e. the metals would not be further oxidised from their original state and the organic material could be separated from the metals in the form of volatiles and char. Pyrolysis experiments were performed in a tube reactor operating at 300, 400 and 500 degrees C. The gas and oil obtained by pyrolysis were analysed by micro-GC (micro-Gas Chromatography) and GC/MS (Gas Chromatography/Mass Spectrometry), respectively. It was found that the gas produced contained a high amount of CO2, limiting the energy recovery from this fraction. The oil consisted of a high concentration of phenolic and aromatic compounds. The solid residue was crushed and fractionated into different particle sizes for further characterization. The pyrolysis temperature of 300 degrees C was found to be insufficient for metal liberation, while the char was easier to crush at tested temperature of 400 and 500 degrees C. The intermediate temperature of 400 degrees C is then suggested for the process to keep the energy consumption low.

Printed circuit boards (PCB) are one of the most challenging fractions of e-waste in terms of material recycling and energy recovery. In this study, pyrolysis of PCBs in inert and steam atmosphere has been investigated as a valuable alternative for energy recovery of the organic fraction with simultaneous recycling of metals. The decomposition of two different PCB fractions has been investigated by means of thermogravimetric analysis (TGA) and lab scale pyrolysis experiments in steam and nitrogen atmospheres. The composition of the gas obtained from the pyrolysis experiments was strongly influenced by the reactive atmosphere. The characterization of the solid residue by X-ray Powder Diffraction (XRD) and scanning electron microscopy (SEM) showed high influence of steam to the migration of the antimony in the produced vapors.

Printed circuit boards (PCB) are one of the most challenging fractions of waste electrical and electronic equipment (WEEE) in terms of recycling due to their complexity and diversity. Pyrolysis seems to be a promising alternative for production of energy carriers from its organic fraction with simultaneous recovery of metals. Reaction atmosphere is among the process parameters that affects the thermal decomposition as well as the products’ formation and distribution. In this study, the decomposition of two different PCB fractions in inert and steam atmospheres has been investigated by means of thermogravimetric analysis (TGA) and lab scale fixed bed reactor experiments. It was found that the decomposition of the tested materials in steam atmosphere starts at lower temperatures and proceeds slower compared to the N2 atmosphere. Moreover, a two-step decomposition has been observed on the PCB sockets fraction due to the fact that high amount of antimony oxide was present, a common additive for improving the flame retardancy, which have been also observed on previous studies (Wu et al., 2014). The presence of steam influence the pyrolysis gas composition and promotes additional vaporisation of antimony as verified by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). Finally, the liquid fraction has been qualitatively analysed using a GC/MS in order to determine the brominated compounds as well as other compounds that are produced from this process.

Aging of pyrolytic liquid during storage changes its chemical and physical properties. The reason for aging is the chemical instability of the liquid, which is not at thermodynamic equilibrium when quenched after pyrolysis. Compounds active in these reactions mainly derivatives from hemicellulose (e.g. acids and carbonyls). In this work, a two-step pyrolysis concept was investigated to separate these compounds in a lower temperature treatment step upstream a conventional pyrolyzer. Different temperatures of the lower temperature treatment was investigated with constant conditions of the conventional treatment. The total liquid yield derived did not vary from pyrolysis in one step. Results show that the two-step pyrolysis process significantly reduces the concentration of organic acids and carbonyls in the liquid product from the second pyrolyzer, which instead are found in the liquid from the lower temperature treatment. Also, the concentration of sugar derivatives from the second step treatment is increased with the temperature of the first step. However, a complete separation of aging active compounds is not possible without sacrificing partial fractions of others (lignin derivatives were found in the low-temperature treatment). By varying the temperature of the first step one can control the concentrations and the liquid yield from each step.