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Bio-oil from biomass pyrolysis is a promising alternative and clean source of biofuels, chemicals, and materials. Its chemical composition, physical and chemical properties, and multiphase behavior change over time, because of aging, which significantly affects its storage, handling, transportation, upgrading, and application. This Review focuses on studying bio-oil aging, and its outlook, primarily covering the following four components: (1) the chemical composition, physical and chemical properties, and multiphase behavior of bio-oil; (2) the indicators for measuring the degree of aging and aging characteristics, including physical and chemical properties change during long-term and accelerated aging of bio-oil; (3) the aging mechanisms and kinetics emphasizing the reactions during the aging process and different kinetic models based on different aging indicators; (4) the potential approaches to slowing bio-oil aging. This Review presents highlights in developing aging mechanisms and kinetics that will allow the reader to have an in-depth understanding of the effect of aging on bio-oil properties and the approaches to improve the resistance of bio-oil aging.

Pyrolysis is a promising and attractive way to convert lignocellulosic biomass into low carbon-emission energy products. To effectively use biomass feedstock with size distribution to produce biofuels, a comprehensive kinetic model of the process, occurring at particle level, is important. In this study, the population balance model (PBM)-distributed activation energy model (DAEM) coupled model is first time developed to predict biomass pyrolysis. The Population balance model is used to present the variable size distribution of solid, decomposed from virgin biomass to porous char. Two different kinetic models are embedded into the conservation equations of mass and energy. They are compared to demonstrate the prediction performance of heating-up time during the pyrolysis process of biomass with a normal size distribution. It is found that non-isothermal kinetics without and with DEAM capture the intra-particle temperature distribution. There is a noticeable difference of heating-up time between single and distributed particle size.

Three series of catalysts consisting of gold (Au), platinum (Pt), or gold-platinum bimetallic nanoparticles (NPs) with controlled sizes (Au NPs 10 &plusmn, 2 nm, Pt NPs 6 &plusmn, 2 nm) anchored on hierarchical micro-/meso-/macroporous silica were successfully developed and systematically evaluated for the selective oxidation of aromatic alcohols to their corresponding aldehydes. The catalysts were prepared by the sol-immobilization method using as-made Au NPs and/or Pt NPs colloids, the silica supports were prepared with controlled pore structures and the hierarchical porous structures of catalysts were created by controllable desilication via the alkaline solution of the metal colloids. The catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS), and these results showed no synergistic effect between Au and Pt on boosting the catalytic performance, whereas they demonstrated a clear dependence of catalytic conversions and reaction rates on the structural porosity of Au-Pt bimetallic catalysts. Our findings could potentially inspire peer researchers and scientists to develop designer porous catalysts and processes in the selective organic conversions.

The kinetic compensation effect between the activation energy and the pre-exponential factor has extensively existed in the thermochemical conversion processes of lignocellulosic biomass. The research on the kinetic compensation effect in lignocellulosic biomass torrefaction has been insufficient yet. The torrefaction of the pinewood sample was experimentally investigated by thermogravimetric analysis (TGA) at five isothermal temperatures of 220, 250, 265, 280 and 295 °C. The reaction order model was used to analyze the isothermal torrefaction kinetics of lignocellulosic biomass, and the results showed that many sets of activation energy and pre-exponential factor could describe the experimental data at each temperature equally well and they excellently satisfied the kinetic compensation effect relationship. The linear regression lines of the kinetic compensation effect points at different temperatures intersected at one point, whose values corresponded to the obtained optimal kinetic parameters. A kinetic-compensation-effect-based method was developed and verified to determine the kinetic parameters of isothermal biomass torrefaction. Based on the optimal kinetic parameters, the thermodynamic parameters (including Gibbs free energy, enthalpy, and entropy) of biomass torrefaction processes at various temperatures were calculated and analyzed.

The bifunctional Ga/HZSM-5 catalyst has been proven having the capability to increase the selectivity of aromatics production during catalytic pyrolysis of furan and woody biomass. However, the reaction chemistry and kinetics of pyrolysis of herbaceous biomass promoted by Ga/HZSM-5 is rarely reported. Pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) analysis and non-isothermal thermogravimetric analysis at four heating rates were carried out to investigate the decomposition behavior and pyrolysis kinetics of corn stalk without and with Ga/HZSM-5. The effective activation energies for corn stalk pyrolysis were calculated by using the Friedman isoconversional method. The Py–GC/MS analysis results indicated that the Ga/HZSM-5 catalyst had a high selectivity toward producing the aromatic chemicals of xylene, toluene and benzene, whereas the major products from non-catalytic pyrolysis of corn stalk were oxygenated compounds. The presence of Ga/HZSM-5 could significantly reduce the effective activation energies of corn stalk pyrolysis from 159.9–352.4 kJ mol−1 to 41.6–99.8 kJ mol−1 in the conversion range of 0.10–0.85.

To ensure a sustainable future, it is imperative to efficiently utilize abundant biomass to produce such as platform chemicals, transport fuels, and other raw materials; hydrochar is one of the promising candidates derived by hydrothermal carbonization of biomass in pressurized hot water. The synthesis of “hydrochar-wrapped Ti3AlC2-derived nanofibers” was successfully achieved by a facile one-pot hydrothermal reaction using glucose as the hydrochar precursor. Meanwhile, cellulose and pinewood sawdust as raw materials were also investigated. Products were characterized by XRD, N2 adsorption-desorption isotherms, SEM, TEM and FT-IR to investigate their crystal structures, textural properties, morphologies, and surface species. In the adsorption test to remove Cd(II) and Cu(II) in aqueous solution, hydrochar-wrapped nanofibers outperformed pure nanofibers derived from Ti3AlC2, hydrothermal carbon derived from glucose and commercial activated carbon. Finally, the regeneration, sorption kinetics, and possible adsorption mechanism were also explored.

The first and nth order kinetic models are usually used to describe cellulose pyrolysis. In this work, the local sensitivities of the conversion and derivative conversion with respect to the frequency factor, the logarithm of the frequency factor, the activation energy and the reaction order for the first and nth order kinetic models are calculated by using the finite difference method. The results show that the sensitivities of the first and nth order kinetic models with respect to the activation energy and the logarithm of the frequency factor are significant, while the frequency factor and the reaction order affect the nth order kinetic model slightly. Compared with the frequency factor, the natural logarithm of the frequency factor is a better choice in the parameter estimation of the first and nth order kinetic models. Graphical Abstract: [Figure not available: see fulltext.]

To explore the mechanism for hydrodeoxygenation (HDO) of bio-oil, which contains large compounds that share similar molecular structures of phenyl ring with oxygen-containing functional groups, guaiacol as a typical model compound of lignin-derived bio-oil was hydrotreated at 150–350 °C under 3–7 MPa (H2) using the synthesized zirconia-supported Rh catalyst in a batch reactor. With Rh/ZrO2 catalyst, guaiacol can be completely converted where reaction temperature plays a decisive role and significantly affects the degree of hydrogenation. HDO Process was optimized with insight into effects of different reaction parameters, including H2 pressure, reactant concentration, reaction time and temperature, on the whole process of HDO and formation of undesired oxygen-contained products. The optimum reaction conditions were 5 wt% guaiacol, 300 °C and 7 MPa in which guaiacol could be completely deoxygenated with 87. 7 mol% oxygen-free product of cyclohexane in 3 h and the desired O/C and H/C ratios of products were obtained. A specific reaction network including three main steps: “guaiacol → 1-methyl-1,2-cyclohexanediol → cyclohexanone and cyclohexanol → completely deoxygenated compounds of cycloalkanes”, was deduced by a comprehensive study on different reaction parameters and a typical key reaction network for HDO of lignin-derived bio-oil is proposed based on model compounds studies. Kinetic model for HDO of guiaacol with the Rh/ZrO2 catalyst was proposed based on the credible pathway and it fits well to a pseudo-first-order kinetic model that the R2 values obtained for the fittings were all above 0.98 at four temperatures. At low temperature of 150 °C, the kinetically relevant step is hydrogenation of the aromatic ring, yielding 90 mol% 1-methyl-1,2-cyclohexanediol, while at high temperature (≥300 °C), the kinetically relevant step is the complete deoxygenation of oxygen-containing functional groups which mainly yields cyclohexane. These results would be helpful to further understand the HDO mechanism of lignin-derived bio-oil, and the excellent performance of Rh/ZrO2 demonstrated its potential application in bio-oil hydrodeoxygenative upgrading process.

The kinetic compensation effect in the logistic distributed activation energy model (DAEM) for lignocellulosic biomass pyrolysis was investigated. The sum of square error (SSE) surface tool was used to analyze two theoretically simulated logistic DAEM processes for cellulose and xylan pyrolysis. The logistic DAEM coupled with the pattern search method for parameter estimation was used to analyze the experimental data of cellulose pyrolysis. The results showed that many parameter sets of the logistic DAEM could fit the data at different heating rates very well for both simulated and experimental processes, and a perfect linear relationship between the logarithm of the frequency factor and the mean value of the activation energy distribution was found. The parameters of the logistic DAEM can be estimated by coupling the optimization method and isoconversional kinetic methods. The results would be helpful for chemical kinetic analysis using DAEM.

The distributed activation energy model (DAEM) has been widely used to analyze the thermal decomposition of solid fuels such as lignocellulosic biomass and its components, coal, microalgae, oil shale, waste plastics, and polymer etc. The DAEM with a single distribution of activation energies cannot describe those reactions well since the thermal decomposition normally involves multiple sub-processes of various components. The double DAEM employs a double distribution to represent the activation energies. The Gaussian distribution is usually used to represent the activation energies. However, it is not sufficiently accurate for addressing the activation energies in the initial and final stages of the thermal decomposition reactions of solid fuels. Compared to the Gaussian distribution, the logistic distribution is slightly thicker at the curve tail and suits better to describe the activation energy distribution. In this work, a theoretical analysis of the double logistic DAEM for the thermal decomposition kinetics of solid fuels has been systematically investigated. After the derivation of the double logistic DAEM, its numerical calculation method and the physical meanings of the model parameters have been presented. Three typical types of simulated double logistic DAEM processes have been obtained according to the overlapped situation of two derivative conversion peaks, namely separated, overlapped and partially overlapped processes. It is found that, for the partially overlapped process, the form of the minor peak (overlapped peak or peak shoulder) depends on the values of the frequency factor and heating rate. Considering the simulated processes and related examples from literature, the double logistic DAEM has been remarked as a more reliable tool with abundant flexibility to explain the thermal decomposition of various solid fuels. More accurate results are expected if the double logistic DAEM is coupled with the computational fluid dynamics (CFD) simulation for those reactions mentioned above.

In this work, co-pyrolysis of Miscanthus Sacchariflorus (MS) and three ranks of coal, namely lignite (LC), bituminous coal (BC), and anthracite (AC), was performed at the analytical scale. The co-pyrolysis kinetic and products were analysed and compared theoretically and experimentally. The results revealed the synergistic effects of the coal characterstics and biomass blend ratio (BBR) on the thermal decomposition and the products in gaseous phase. The co-pyrolysis of MS-LC and MS-BC samples was characterised by three distinct stages, which were sequentially dominated by moisture removal, decomposition of MS and decomposition of coal. The activation energies of the co-pyrolysis process were different from the activation energies of the pyrolysis of individual MS and coal samples. The kinetics analysis showed that increasing the BBR increased the activation energies of the MS-coal blends up to 25% at the temperatures below 350 °C. However, at the higher temperature range, it decreased the activation energies of MS-LC and MS-BC blends but increased those of MS-AC blends. Both of the coal rank and BBR had noticeable impacts on the thermal behaviour during co-pyrolysis. The optimum positive synergistic effects were obtained on MS-LC blend with a BBR of 1:1. The FTIR analysis results showed the evolution profiles of CH4, CO, CO2, water, formic acid, phenol and xylene. All the products analysed showed L-peaks (250–400 °C) corresponding to MS decomposition. Increasing the BBR promoted the release of all the analysed products from MS-LC and MS-BC, indicating the synergistic effect of the co-pyrolysis.