Peng Liu

Efficient conversion of biomass tar, together with effective fixation and valorization of carbon dioxide (CO2), remains a major challenge in renewable energy. Addressing this challenge requires a fundamental understanding of the atomic-scale mechanisms governing CO2-assisted catalytic tar reforming over bimetallic catalysts, which remain poorly understood despite extensive reports on macroscopic catalytic performance. Herein, multiscale characterization is integrated with density functional theory (DFT) calculations to unravel the synergistic interplay between Ni-Fe alloy and HZSM-5 acid sites in CO2-activated toluene cracking, a representative biomass tar model compound. Three previously unrecognized mechanistic insights are revealed: (i) CO2 modulates the electronic structure of Ni through Fe-mediated charge transfer, as evidenced by XPS binding energy shifts; (ii) the Boudouard reaction proceeds with an activation barrier of 1.98 eV, quantitatively accounting for the observed 66% reduction in coke deposition; and (iii) CO2 shifts the reaction pathway toward monocyclic aromatic hydrocarbons by lowering the Gibbs free energy of polycyclic aromatic hydrocarbon (PAH) condensation, resulting in a 22% increase in selectivity. Experimentally, the Ni-Fe/HZSM-5 catalyst achieves a syngas yield of 323.3 mL/g-toluene at 900 °C with a hydrogen selectivity of 56.2%, while catalyst stability is enhanced more than threefold through coke removal via the Boudouard reaction. Comprehensive characterization combined with DFT calculations further demonstrates that Fe promotes the dispersion of active Ni sites and enhances CO2 activation capability. Collectively, this work establishes a mechanistic blueprint for the rational design of coke-resistant bifunctional catalysts and provides fundamental mechanistic insights into the in situ tar removal and hydrogen production during biomass gasification, extending the applicability of CO2-assisted reforming strategies beyond biomass tar to broader hydrocarbon conversion processes.

This study systematically investigated the effects of torrefaction at 220, 260, and 300 ℃ on the structural evolution, thermal stability, and pyrolysis behavior of kraft lignin (KL), aiming to provide insights for its valorization. KL was pretreated in a fixed-bed reactor and characterized using proximate/ultimate analyses, Fourier Transform Infrared Spectroscopy (FTIR), Carbon-13 Nuclear Magnetic Resonance Spectroscopy (13C NMR), and Thermogravimetric Analysis (TG). Results revealed that increasing torrefaction temperature reduced the solid yield to 58.36%, while significantly enhancing the fixed carbon content, decreasing O/C and H/C ratios to 0.11 and 0.52, and increasing the high heating value (HHV) to 25.26 MJ/kg, indicating pronounced deoxygenation and carbon enrichment. FTIR and 13C NMR analyses showed that the content of unstable ether linkages decreased from 22.22% to 5.51%, and aromatic carbon increased to 42.68%, and Car-Car bond concentration rose continuously, reflecting the combined effects of β-O-4 ether bond cleavage, demethoxylation, dehydration, and aromatization-condensation. TG analysis demonstrated substantially improved thermal stability, with Ti, Tm, and Tt increasing from 259, 358, and 506 ℃ to 374, 532, and 785 ℃, respectively. Pyrolysis experiments further indicated that torrefied KL reduced CO2 yield to 32.83 mL/g while maintaining a solid yield of 37.68%, which successfully enhanced the stability of the lignin carbon framework and improved its carbon sequestration capacity. Overall, torrefaction effectively optimized the chemical structure and bond network of KL, enhancing thermal stability, directing pyrolysis pathways, and improving carbon sequestration potential during energy-oriented biomass utilization, offering an effective approach for carbon mitigation.

Solid oxide fuel cell power generation systems are devices that utilize solid electrolytes to transfer ions for electrochemical energy conversion. A wide range of gases can be used as fuel gas, including hydrogen, natural gas, and carbon monoxide. Considering the high cost of pure hydrogen, hydrogen production from natural gas reforming has become a hot research area. In this study, the 4F-LCA method was employed to construct an evaluation framework, with a particular emphasis on the cost analysis of solid oxide fuel cell power generation systems, and uses a bottom-up approach to build a system economic analysis model to visualize the major costs involved in the system. An economic benefit analysis and sensitivity analysis were carried out for the 2 kW natural gas solid oxide fuel cell as a case by taking the financial net present value (NPV), internal rate of return (IRR) and payback period into account. In this study, the investment cost and payback period of a 2 kW solid oxide fuel cell system are obtained, which can provide a reference for the project construction and operation of solid oxide fuel cell systems.

The thermo-chemical conversion of biomass wastes is a practical approach for the value-added reclamation of bioenergy in large quantities, and pyrolysis plays a core role in this process. In this work, poplar (PR) and cedar (CR) were used as staple wood biomasses to investigate the apparent kinetics of TG/DTG at different heating rates. Secondly, miscellaneous wood chips (MWC), in which PR and CR were mixed in equal proportion, were subjected to comprehensive investigations on their pyrolysis behavior and product evolution in a fixed bed reactor with pyrolysis temperature, catalyst, and the flow rate H₂O steam as influencing factors. The results demonstrated that both PR and CR underwent three consecutive pyrolysis stages, the TG/DTG curves shifted to higher temperatures, and the peak temperature intervals also enhanced as the heating rate increased. The kinetic compensation effect expression and apparent reaction kinetic model of CR and PR pyrolysis were obtained based on the law of mass action and the Arrhenius equation; the reaction kinetic parameter averages of Ea and A of its were almost the same, which were about 72.38 kJ/mol and 72.36 kJ/mol and 1147.11 min⁻¹ and 1144.39 min⁻¹, respectively. The high temperature was beneficial for the promotion of the pyrolysis of biomass, increased pyrolysis gas yield, and reduced tar yield. This process was strengthened in the presence of the catalyst, thus significantly increasing the yield of hydrogen-rich gas to 117.9 mL/g_-biomass. It was observed that H₂O steam was the most effective activator for providing a hydrogen source for the whole reaction process, promoted the reaction to proceed in the opposite direction of H₂O steam participation, and was beneficial to the production of H₂ and other hydrocarbons. In particular, when the flow rate of H₂O steam was 1 mL/min, the gas yield and hydrogen conversion were 76.94% and 15.90%, and the H₂/CO was 2.07. The yields of H₂, CO, and CO₂ in the gas formation were significantly increased to 107.35 mL/g_-biomass, 53.70 mL/g_-biomass, and 99.31 mL/g_-biomass, respectively. Therefore, H₂ was the most dominant species among gas products, followed by C-O bond-containing species, which provides a method for the production of hydrogen-rich gas and also provides ideas for compensating or partially replacing the fossil raw material for hydrogen production.

Melamine-impregnated paper waste (MIPW) is an unavoidable byproduct of the melamine-impregnated paper production process, and it must be urgently disposed. In this paper, due to its high N content, MIPW was used as a N source to co-pyrolyze with camellia oleifera shell (COS). By changing the proportion of MIPW in the raw materials, the migration path of the N was studied during the co-pyrolysis process. X-ray photoelectron spectroscopy (XPS), elemental analysis (EA), total nitrogen analysis (TN) and ultraviolet spectrophotometry were used to determine the content and the types of N-containing components in raw materials and products. The results showed that during the co-pyrolysis process, the N in MIPW and COS would be converted into different types of N-containing components, and the proportion of MIPW in raw materials directly impacts the product distribution and the N migration path. With the increase in the proportion of MIPW from 10 to 50 wt.% (daf, mass ratio), the proportion of N in raw materials that migrated into the solid phase decreased from 27.58 to 16.31 wt.%, while that which migrated to the gas and liquid phases increased from 24.92 and 47.50 wt.% to 25.97 and 57.72 wt.%, respectively. The proportions of N in the raw materials that changed into pyridinic-N, pyrrolic-N and graphitic-N in the solid phase and N₂-N in the gas phase were decreased. The proportions of NH₃-N and HCN-N in the gas phase and NH₃-N and organic-N in the liquid phase were increased. Moreover, synergies were observed during the co-pyrolysis process, which affected the N migration path in the raw material. This study will provide policy directions and theoretical support for the comprehensive utilization of MIPW and COS.

The goal of this research was to investigate the effects of torrefying temperature (220, 260, and 300 °C) on the physicochemical properties, kinetics, thermodynamic parameters, and reaction processes of Acer palmatum (AP) during the pyrolysis process. The kinetics of raw materials and torrefied biomass were studied by using three kinetic models, and the main function graph approach was employed to find the reaction mechanism. The torrefied biomass produced at temperatures of 220 °C (AP-220), 260 °C (AP-260), and 300 °C (AP-300) was thermogravimetrically analyzed at four different heating rates (5, 10, 15, and 20 °C/min). In comparison to the raw material, the average activation energy of torrefied biomass declined with increasing temperature, from 174.13 to 84.67 kJ/mol (FWO), 172.52 to 81.24 kJ/mol (KAS and DAEM). The volatile contents of AP and AP-220 are higher than those of AP-260 and AP-300, indicating that the random nucleation model occupies the central position. Compared with the raw biomass, the average Gibbs free energy (ΔG) of torrefied biomass increased from 157.97 to 195.38 kJ/mol. The mean enthalpy change (ΔH) during the torrefaction process is positive, while the mean entropy change (ΔS) of the torrefaction of biomass is negative, decreasing from 16.93 to -151.53 kJ/mol (FWO) and from 14.36 to -156.06 kJ/mol (KAS and DAEM). Overall, the findings provide a comprehensive understanding of the kinetics and improved features of torrefied biomass as a high-quality solid fuel.

It is important to clarify the distribution of pyrolysis products from lignocellulosic biomass for its thermal transformation to produce high-quality bio-oil. Influences of the reaction temperature and catalysts on the pyrolysis product distribution from aspen wood (AW) and rice husk (RH) were studied by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The difference in components from the lignocellulosic biomass results in different pyrolysis characteristics of the biomass raw materials. The reaction temperature significantly influences the product distribution from AW and RH pyrolysis. In all AW catalysis experiments, acids (8.35%), ketones (3.79%), phenols (4.73%), and esters (1.50%) have the lowest content while carbohydrates (48.75%) demonstrate the highest content when taking zinc chloride (ZnCl₂) as the catalyst; the HZSM-5 molecular sieve (HZSM-5) promotes the generation of esters (7.97%) and N-compounds (22.43%) while inhibiting production of aldehydes (2.41%); addition of an MCM-41 molecular sieve (MCM-41) is conducive to increasing the contents of aldehydes (21.29%), furans (5.88%), ketones (22.30%), acids (20.46%), and hydrocarbons (4.85%), while reducing the contents of alcohols (0) and carbohydrates (0). In all RH catalysis experiments, the addition of ZnCl₂ helps increase the content of carbohydrates (39.16%) and decrease the contents of ketones (3.89%), phenols (5.20%), alcohols (2.34%), esters (1.13%), and N-compounds (3.09%); when applying HZSM-5 as the catalyst, hydrocarbons (18.28%) and alcohols (6.66%) reach their highest content while acids (13.21%) have the lowest content; MCM-41 promotes the generation of aldehydes (25.33%) and furans (5.55%) while inhibiting that of carbohydrates (1.42%).

In this study, Baoqing lignite (BL) and rice straw (RS), which were the representatives of low-rank coal and biomass, were co-thermally oxidized to produce composite humic substances (HS), including humic acid (HA) and fulvic acid (FA). Taking HS content as the output response, the co-thermally oxidizing conditions were optimized through single factor experiment and response surface methodology (RSM). The structures of HA and FA prepared under optimized conditions were analyzed by SEM, UV, and FTIR. Results showed that HS content was clearly influenced by the material ratio, oxidation time, and oxidation temperature, as well as their interactions. The optimized co-thermal oxidization condition was as follows: BL and RS pretreated with a material ratio of 0.53, oxidation time of 59.50 min, and oxidation temperature of 75.63 °C. Through verification, the experimental value (62.37%) had a small relative error compared to the predicted value (62.27%), which indicated that the developed models were fit and accurate. The obtained HA had a tightly packed block structure; FA had a loosely spherical shape. The molecular weight of FA was 2487 Da and HA was 20,904 Da; both had a smaller molecular weight than that reported in other literature. FA showed strong bands at 1720 cm⁻¹, thus confirming the presence of more oxygen-containing functional groups. The appearance of double peaks at 2900~2980 cm⁻¹ indicated that HA contains more aliphatic chains. The co-thermal oxidation of BL and RS gives a new method for the synthesis of HS, and the optimization of co-thermal oxidation conditions will provide fundamental information for the industrialization of composite HS.

Torrefaction is an effective method for upgrading biomass. Cedar torrefaction is carried out in a fixed bed reactor at the temperature of 200–300 °C. The structural parameters are obtained from elemental analysis and ¹³C nuclear magnetic resonance (NMR). Thermal degradation behavior of raw and torrefied cedar is monitored by thermogravimetry analysis. The results show that carbon structure varied during torrefaction has a significant effect on thermal degradation of cedar. Some unstable oxygen functional groups, such as C1 of hemicellulose, β-O-4 linked bonds, and amorphous C6 of cellulose, are decomposed at mild torrefaction of torrefied temperature ≤ 200 °C. The temperature of maximum weight loss rate increases from 348 °C of raw cedar to 373 °C of C-200. The amorphous cellulose is partly re-crystallized at moderate torrefaction of torrefied temperature 200–250 °C. The aromaticity of torrefied cedar increases from 0.45 of C-200 to 0.73 of C-250. The covalent bond in the side chain of aromatic rings in cedar was further broken during torrefaction at severe torrefaction of torrefied temperature 250–300 °C. The area percentage of DTG mainly signed at 387 °C of C-300. The proton aromatic carbon increases from 12.35% of C-250 to 21.69% of C-300. These results will further facilitate the utilization of biomass for replacing fossil fuel to drive carbon neutrality.