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Highlights • Interactions among bio-oil fractions influence the coking mechanisms obviously. • Structure of cokes generated from bio-oil was strongly affected by the interactions. • Cokes from bio-oil are not simple mixture of cokes from bio-oil fractions. • Interactions increase the C O, O H and C O functional groups in cokes. • Interactions promote the O-containing species to be transformed into the cokes. Abstract Coke formation is one major problem during thermal conversion of bio-oil and its main components. Fundamental knowledge about the evolution of the structure of cokes is a prerequisite towards a deep understanding of coking of bio-oil. This study investigates the structure (morphology, elemental composition, O-containing functional groups and aromatic structures) of cokes generated from the pyrolysis of aromatic-rich fraction (ARF) and the aromatic-poor fraction (APF) of bio-oil. The effects of interactions of ARF and APF on properties of the coke formed during the pyrolysis of bio-oil are also studied. The results show that the cokes from the pyrolysis of APF (APF-cokes) are sponge-like while the cokes from the pyrolysis of ARF (ARF-cokes) have a dense structure. The matrix of cokes from the pyrolysis of the whole bio-oil (oil-cokes) is similar to the matrix of ARF-cokes, while its surface is similar to that of APF-cokes, which should be due to the interactions between different bio-oil fractions. The APF-cokes contain more C O, O H and C O functional groups than the ARF-cokes due to the higher O content of APF. Moreover, the interactions between ARF and APF can promote more O-containing species to be transformed as C O, O H and C O functional groups in the oil-cokes. The aromatic rings of ARF-cokes and APF-cokes can be cracked to form smaller ring systems at 300–500 °C, while it is opposite for the oil-cokes because the aromatic structures formed via the interactions between ARF and APF are more stable. At higher temperatures (>500 °C), the interactions (e.g. self-gasification) lead to the highly condensed cokes, while the secondary cokes, which are spherical particles, are preferentially consumed by the steam. [ABSTRACT FROM AUTHOR]

This study focuses on the effects of interactions among bio-oil components on the formation of aromatic structures of bio-oil during its thermal treatment processes at various temperatures and heating rates. A bio-oil sample and its extracted fractions were pyrolyzed in a fixed-bed reactor at 300–800 °C at different temperatures and heating rates. The results show that the pyrolytic products (including the yields and aromatic structures) from raw bio-oil and its extracted fractions are significantly different, which proves the existence of the interactions between the aromatic components and light components of the bio-oil. Additionally, those interactions are determined by the pyrolysis temperature and heating rate to different extents, which further leads to the evolution of aromatic structures during the pyrolysis of bio-oil. For example, owing to the presence of the aromatic-poor fraction, the aromatic compounds (especially ≥ 2 rings) from the pyrolysis of bio-oil are less than that of the aromatic-rich fraction at relatively low temperatures (≤ 500 °C), especially at slow heating rates. This is because the polymerization, as the main interactions, promotes the transformation of more aromatic compounds (over wide range of ring sizes) into coke at these conditions. At fast heating rates, among the complex interactions, the self-gasification of bio-oil is intensified at high temperatures (≥ 700 °C), resulting in lower secondary coke yields and tar yields as well as the concentration of aromatic compounds (especially ≥ 2 rings). [ABSTRACT FROM AUTHOR]

Highlights • Cokes generated at slow heating rates are imporous with smooth surface. • The radical concentration of cokes reaches highest at 600 °C then decreases rapidly. • Interactions among bio-oil components bring the O-functional groups into the coke. • The cokes are more condensed with bigger aromatic rings at high temperatures. Abstract Coke can be formed once the bio-oil was heated, even at very low temperatures, causing almost always serious problems in the upgrading and direct utilization of bio-oil. To minimize the negative impacts from coke formation, the key point is to fully understand the formation and evolution of coke during the thermal treatment of bio-oil. Thus, in this study, the cokes formed from the pyrolysis of bio-oil at different temperatures (300–800 °C) and heating rates were characterized by using a range of advanced analytical instruments. The evolution of cokes (e.g. morphology, elemental composition, chemical structure and concentration of radicals) with increasing temperature and heating rate was traced. The results show that the cokes generated at slow heating rates are imporous with smooth surface but porous at high temperatures and fast heating rates. The radical concentration of the cokes reaches the highest level at 600 °C, then decreases rapidly with further increasing temperature to form more free radicals, which promote the condensation reaction of aromatic systems to form larger ring structures of the coke at high temperatures, with lower H/C and O/C ratios. The O-containing functional groups could be brought into the coke via the interactions between light and heavy components of bio-oil. [ABSTRACT FROM AUTHOR]

[Display omitted] • Coke formation during bio-oil pyrolysis was inhibited via Ni/Al 2 O 3 mixing. • Influence of Ni/Al 2 O 3 mixing on aromatic structures of products was investigated. • Interaction among AF, LDO and Ni/Al 2 O 3 during bio-oil pyrolysis was revealed. • Mechanism for bio-oil pyrolysis with Ni/Al 2 O 3 mixing was proposed. Bio-oil can be converted to chemicals, carbon material, or syngas by various thermochemical processes which are always preceded with the pyrolysis step. In bio-oil pyrolysis, coke formation is almost inevitable, causing difficulties for further processing. In this study, bio-oil was mixed with Ni/Al 2 O 3 before it was fed for pyrolysis. Interesting results were observed whereby the effect of Ni/Al 2 O 3 mixing on coke formation shifted from promoting to inhibiting with increasing pyrolysis temperature. When the temperature was higher than 700 °C, contrary to the cases without mixing, the apparent decreases in coke yield were observed (e.g., the coke yield decreased by 10% at 800 °C). Comparative studies on bio-oil and its lignin-derived oligomer fraction indicated that the catalytic cracking of small molecules could enhance the formation of hydrogen radicals, which promoted thermal decomposition of lignin-derived oligomers, thus inhibiting coke formation via polymerization. [ABSTRACT FROM AUTHOR]

[Display omitted] • Polymerization electro-initiates on cathode surface, and propagates in bio-oil bulk phase. • Large molecules (MW > 800 Da) originally existed in bio-oil contributes to polymerization. • Aromatics, furans and levoglucosan are important polymerization reactants. • Increasing reaction time and current density can enhance polymerization of bio-oil. • Polymer layer forms on anode surface by polymerization. The electrochemical method provides a green route to upgrade bio-oil, but it is still challenged by the issue of bio-oil polymerization which restrains its application. This study investigates the polymerization behaviors of the bio-oil during its electrochemical upgrading under various current densities and different reaction time using macrophotography and multiple characterizations. The results show that the polymerization is not only electro-initiated on the cathode surface, but also electro-propagated in the bulk solution. The large molecules (MW > 800 Da) originally existed in the bio-oil are consumed in the polymerization. The small molecules (MW < 800 Da) can be produced from the polymerization of aromatics with 1–3 rings, furans and levoglucosan through cycloaddition, dehydration and demethoxylation. These small molecules can directly form solid products (coke) rather than leading to the increase of the large molecules. The polymerization can be enhanced by the increasing current density and reaction time. The rate of bio-oil polymerization can surpass the rate of coke formation as the reaction proceeds. The polymer layer also forms on the anode surface by polymerization during the electrochemical upgrading of bio-oil. [ABSTRACT FROM AUTHOR]

Highlights • Effect of pre-reforming by Fe/bio-char catalyst on bio-oil reforming was studied. • Fe/bio-char pre-reforming increases the H 2 and CO yields from bio-oil reforming. • Fe/bio-char catalyst promotes the transformation of aromatics into light compounds. • Less coke was formed on Ni-based catalyst due to Fe/bio-char catalyst at 550–600 °C. • Pre-reforming promotes the formation of NiO and NiAl 2 O 4 on Ni-based catalyst. Abstract Ni-based catalyst is prone to the deactivation by coke deposition during the catalytic steam reforming of bio-oil. In order to optimize catalytic activity of the Ni-based catalyst, a two-stage catalytic reforming scheme was proposed whereby a low-temperature (350–600 °C) pre-reforming process with a less expensive catalyst was introduced prior to the Ni-based catalyst. To study this scheme, the reforming experiments with different combinations of Fe/bio-char (in the first stage) and Ni-Ca/γ-Al 2 O 3 (in the second stage) were conducted. In addition to the quantification of product yields, the tar and gas were characterized with an ultraviolet (UV) fluorescence spectroscopy, a gas chromatography/mass spectrometer (GC/MS) and a gas chromatography (GC). The results indicate that significant proportions of naphthalenes and polycyclic aromatics in the intermediate volatiles turned into furans, phenols and non-aromatics, which are easier to be reformed on Ni-based catalysts, via the Fe/bio-char pre-reforming, resulting in the increase of the final H 2 and CO yields of the overall process. At high pre-reforming temperatures (550–600 °C), the coke formation on Ni-based catalyst was significantly inhibited due to the Fe/bio-char pre-reforming. In addition, the results indicate that the spent Ni-based catalyst had more free NiO and NiAl 2 O 4 spinel than the fresh one, suggesting that the increase in the catalytic activity of Ni-based catalyst during the reforming process was promoted by Fe/bio-char pre-reforming. [ABSTRACT FROM AUTHOR]

Bio-oil from the fast pyrolysis of biomass can be converted to solid carbon materials, chemicals and syngas by various thermochemical conversion methods. As a first step in all of these processes, bio-oil undergoes drastic components changes due to its exposure to the elevated temperature. Understanding the effects of heating rate on bio-oil transformation during its pyrolysis is therefore crucial for effective utilization of bio-oil. In this study, a bio-oil sample produced from the fast pyrolysis of rice husk at 500 °C was pyrolyzed in a fixed-bed reactor at temperatures between 300 and 800 °C at three different heating rates: fast (≈200 °C/s), medium (≈20 °C/s), and slow (≈0.33 °C/s). In addition to the quantification of coke and tar yields, the tar was characterized with an ultraviolet (UV) fluorescence spectroscopy, a gas chromatography/mass spectrometer (GC/MS) and a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). Our results indicate that slow heating rates promote polymerization of bio-oil components, particularly at low temperatures (<500 °C), resulting in higher primary coke yields than that of the fast heating rates. Decomposition reaction was found to be pronounced at fast heating rates, causing decreases in the tar yields and abundance of light compounds. The increases in the yields of the secondary coke, the formations of more condensed aromatic structures and macromolecules ( m / z  > 500) were also promoted at fast heating rates via the more intense secondary reactions. [ABSTRACT FROM AUTHOR]

The electrochemical method is becoming a promising approach to deliver the bio-oil upgrading objective at room temperature. However, it still faces the coke formation issue because of the easy polymerization nature of bio-oil. Interactions among components impact the polymerization during the electrochemical upgrading of bio-oil. This study investigates the effects of interactions between the aromatic-rich and aromatic-poor fractions (ARFs and APFs) of the bio-oil on polymerization under various reaction time and current densities. Coke yield differences provide direct evidence of the existence of interactions between ARFs and APFs during the electrochemical upgrading process. Our results indicate that the coke yields and its condensation level are decreased by the interactions. The surface area, pore volume and the functionalities content of the coke are increased by the interactions. In addition to polymerization, more types of reactions including hydrogenation and esterification are induced by the interactions, resulting in more types of products and less coke. The interactions can inhibit polymerization by consuming the coke precursors before their condensation. The interactions can also inhibit the anodic adsorption and oxidation, thus depressing polymerization and coke formation. Investigating the impacts of interactions between aromatic-rich and aromatic-poor fractions on polymerization of bio-oil in chronoamperometric electrochemical upgrading. [Display omitted] • Interactions of aromatic-rich and -poor fractions in bio-oil is proven existed in electrolysis. • Aromatic-poor fractions end-cap the reactive chains of polymerization precursors. • Interactions weaken the anodic adsorption and polymerization of bio-oil. • Interactions decrease the yields, surface areas and pore volumes of the coke. [ABSTRACT FROM AUTHOR]

• Fe/activated char shows high performance on bio-oil upgrading. • The fresh catalysts favor the production of aromatic hydrocarbons. • The regenerated catalysts by active agents facilitate the production of phenols. • The catalyst regeneration promotes the formation of γ-Fe 2 O 3 on the char surface. Char-supported metals as catalysts has attracted much attention due to the renewability and structural controllability of char. However, such catalysts can not be regenerated by the conventional calcination method, which is widely used in industy. In this study, the catalytic performance of char-supported Fe on bio-oil upgrading during pyrolysis of pine wood was first investigated. It was found that the typical components (acids, ketones, furans, etc) in bio-oil were completely converted to aromatic hydrocarbons over char-supported Fe, in which char acted not only as a support but also as a catalyst for the converison of bio-oil to phenols. Then, the spent char-supported Fe catalyst was regenerated by CO 2 or steam gasification. The results showed that only phenols could be produced over both CO 2 and steam regenerated catalysts, which was caused by the changes in carbon structure and surface functional groups of char as well as the species of Fe. The CO 2 regenerated catalyst was rich in C O groups and α-Fe 2 O 3 , while the H 2 O regenerated one mainly contained O C O groups and Fe/FeO. [ABSTRACT FROM AUTHOR]

Abstract: Bark constitutes an important part of any woody biomass to be used for the production of second generation biofuels and chemicals. Pyrolysis followed by biorefinery is a promising technology for the efficient utilisation of all components from a woody crop. While significant efforts have been devoted to the investigation of the pyrolysis characteristics of wood, relatively less is known about the pyrolysis behaviour of bark. This study aims to clarify the effects of temperature on the yields and composition of bio-oil from the pyrolysis of eucalypts bark. The bark of mallee, a type of eucalypt grown for soil amendment in Western Australia, was pyrolysed between 300 and 580°C at fast heating rates in a fluidised-bed pyrolysis unit. The bio-oil liquid products separate into two phases. The bio-oil liquid products were analysed by GC–MS, Karl-Fischer titration, UV-fluorescence spectroscopy, ICP-OES and thermogravimetric analysis (TGA). These results are compared, when appropriate, to those obtained from the wood fraction. [Copyright &y& Elsevier]