Chemical analysis and reactivity of biomass pyrolysis products. Application to the development of carbon-neutral biofuels and chemicals

In this dissertation the pyrolytic conversion of biomass into chemicals and fuels was investigated from the analytical point of view. The study was focused on the liquid (bio-oil) and solid (char) fractions obtainable from biomass pyrolysis. The drawbacks of Py-GC-MS described so far were partially solved by coupling different analytical configurations (Py-GC-MS, Py-GC-MIP-AED and off-line Py-SPE and Py-SPME-GC-MS with derivatization procedures). The application of different techniques allowed a satisfactory comparative analysis of pyrolysis products of different biomass and a high throughput screening on effect of 33 catalysts on biomass pyrolysis. As the results of the screening showed, the most interesting catalysts were those containing copper (able to reduce the high molecular weight fraction of bio-oil without large yield decrease) and H-ZSM-5 (able to entirely convert the bio-oil into “gasoline like” aromatic products). In order to establish the noxious compounds content of the liquid product, a clean-up step was included in the Py-SPE procedure. This allowed to investigate pollutants (PAHs) generation from pyrolysis and catalytic pyrolysis of biomass. In fact, bio-oil from non-catalytic pyrolysis of biomass showed a moderate PAHs content, while the use of H-ZSM-5 catalyst for bio-oil up-grading determined an astonishing high production of PAHs (if compared to what observed in alkanes cracking), indicating an important concern in the substitution fossil fuel with bio-oil derived from biomass. Moreover, the analytical procedures developed in this thesis were directly applied for the detailed study of the most useful process scheme and up-grading route to chemical intermediates (anhydrosugars), transportation fuels or commodity chemicals (aromatic hydrocarbons). In the applied study, poplar and microalgae biomass were investigated and overall GHGs balance of pyrolysis of agricultural residues in Ravenna province was performed. A special attention was put on the comparison of the effect of bio-char different use (fuel or as soil conditioner) on the soil health and GHGs emissions.

Biochar characterization for its environmental and agricultural utilization. Occurrence, distribution and fate of labile organic carbon and polycyclic aromatic hydrocarbons

In this thesis the potential risks associated to the application of biochar in soil as well the stability of biochar were investigated. The study was focused on the potential risks arising from the occurrence of polycyclic aromatic hydrocarbons (PAHs) in biochar. An analytical method was developed for the determination of the 16 USEPA-PAHs in the original biochar and soil containing biochar. The method was successfully validated with a certified reference material for the soil matrix and compared with methods in use in other laboratories during a laboratory exercise within the EU-COST TD1107. The concentration of 16 USEPA-PAHs along with the 15 EU-PAHs, priority hazardous substances in food, was determined in a suite of currently available biochars for agricultural field applications derived from a variety of parent materials and pyrolysis conditions. Biochars analyzed contained the USEPA and some of the EU-PAHs at detectable levels ranging from 1.2 to 19 µg g-1. This method allowed investigating changes in PAH content and distribution in a four years study following biochar addition in soils in a vineyard (CNR-IBIMET). The results showed that biochar addition determined an increase of the amount of PAHs. However, the levels of PAHs in the soil remained within the maximum acceptable concentration for European countries. The vineyard soil performed by CNR-IBIMET was exploited to study the environmental stability of biochar and its impact on soil organic carbon. The stability of biochar was investigated by analytical pyrolysis (Py-GC-MS) and pyrolysis in the presence of hydrogen (HyPy). The findings showed that biochar amendment significantly influence soil stable carbon fraction concentration during the incubation period. Moreover, HyPy and Py-GC-MS were applied to biochars deriving from three different feedstock at two different pyrolysis temperatures. The results evidenced the influence of feedstock type and pyrolysis conditions on the degree of carbonisation.

Electrochemistry of polycyclic aromatic molecules for advanced carbon nanostructures: luminescence and transistor applications

Polycyclic aromatic hydrocarbons (PAHs) are a large class of π-conjugated organic molecules with fused aromatic rings, which can be considered as fragments of 2D-graphene and have been extensively studied for their unique optical and electronic properties. The aim of this study is to understand the complex electrochemical behaviour of planar, curved, and heteroatom doped polycyclic aromatic molecules, particularly focusing on the oxidative coupling of their radical cations and the electrochemically induced cyclodehydrogenation reactions. In the first part of this thesis, the class of PAHs and aromatic nanostructures are introduced, and the reactivity of electrogenerated species is discussed, focusing on the electrochemical approach for the synthesis of extended π-conjugated structures. Subsequently, the electrochemical properties and reactivity of electrogenerated radical ions of planar and curved polyaromatics are correlated to their structures. In the third chapter, electrochemical cyclodehydrogenation of hexaphenylbenzene is used to prepare self-assembled hexabenzocoronene, directly deposited on an interdigitated electrode, which was characterised as organic electrochemical transistor. In the fourth chapter, the electrochemical behaviour of a family of azapyrene derivatives has been carefully investigated together with the electrogenerated chemiluminescence (ECL), both by ion-annihilation and co-reactant methods. Two structural azapyrene isomers with different nitrogen positions are thoroughly discussed in terms of redox and ECL properties. Interestingly, the ECL of only one of them showed a double emission with excimer formation. A detailed mechanism is discussed for the ECL by co-reactant benzoyl peroxide, to rationalise the different ECL behaviours of the two isomers on the basis of their topologically modulated electronic properties. In conclusion, the different electrochemical behaviours of PAHs were shown, focussing on the chemical reactivity of the electrogenerated species and taking advantage of it for important processes spanning from unconventional synthesis methods for carbon nanostructures to the exploitation of self-assembled nanostructured systems in organic electronics, to novel organic emitters in ECL.

Liquid biofuels for aviation: valorisation of the by-product biochar

Biochar is a carbonaceous material produced through pyrolysis of biomass. One promising application of biochar is phosphorus recovery from wastewater. Phosphorus is a vital nutrient for plant growth, but its use in fertilizers often leads to runoff or leaching. Wastewater treatment plants discharge large amounts of phosphorus-rich wastewater, contributing to eutrophication and ecological harm. Biochar can sorb phosphorus, retaining it in solid form. In this thesis, two composites made of biomass and dolomite or shells exhibited superior phosphate sorption compared to biochar alone, reaching up to 100% sorption. Biochar also finds use in soil remediation, specifically in cleaning up contaminated soil. Polycyclic aromatic hydrocarbons (PAHs), which can be carcinogenic and toxic, can be present in soil. Biochar adsorb PAHs, preventing their leakage or bioaccumulation. Hetero-PAHs, a subclass of PAHs with nitrogen, sulfur, or oxygen atoms in their ring structures, are particularly challenging to degrade. Little is known about their behavior or sorption onto biochar. In this thesis, biochar and activated carbon were effective in immobilizing PAHs and hetero-PAHs in real soils, with rates of immobilization reaching 100%. Biochar performed equally or better than activated carbon, offering a cost-effective alternative due to its lower price. Biochar reduce of metal(loid)s mobility in soil. Metal(loid)s like lead, zinc, and arsenic can contaminate soil through industrial sources, agricultural runoff, and other pollution, and are toxic to plants and animals, rendering the soil unsuitable for agriculture. When biochar is added to contaminated soil, it binds to metal(loid)s, preventing leaching into the environment. A biomass-dolomite composite was compared to activated carbon for immobilizing metal(loid)s in contaminated soils. The composite generally outperformed activated carbon and exhibited the ability to immobilize arsenic. In summary, biochar shows promise for phosphorus recovery, soil remediation, and reducing the mobility of heavy metals, offering cost-effective and sustainable solutions to these environmental challenges.