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The objective of current study is to explore the energy recovery potential of fermentation residues. In this perspective, pyrolysis characteristics, kinetics, and modified biochar derived from pine sawdust after fermentation (FPD) were determined, and comparison was established with pine sawdust (PD). The variation range of comprehensive pyrolysis index (CPI) values of FPD was found 6.51 × 10 -7 -16.38 × 10 -7 % 2 ·min -2 ·°C -3 , significantly higher than that of untreated samples determined under the same experimental conditions. The average activation energy of FPD was 367.95 kJ/mol, 389.45 kJ/mol, and 346.55 kJ/mol calculated by Flynn-Wall-Ozawa (FWO) method, Kissinger-Akahira-Sonuse (KAS), and Starink method respectively, and importantly, these values are much higher than those of PD. Additionally, fermentation could enhance the adsorption capacity for methylene blue of biochar from 0.76 mg/g to 1.6 mg/g due to the abundant surface functional groups and three-dimensional internal pore structure. The adsorption pattern of fermented pine wood shifted from chemisorption dominated to the synergetic adsorption of surface functional groups adsorption and intragranular filling. These results show that FPD has favorable pyrolytic properties, and the derived biochar has adsorption properties, which is the basis for designing pyrolysis process and reusing fermentation residues. HIGHLIGHTS: The FPD has higher values of CPI and activation energy than the PD. FPD-derived biochar has higher adsorption capacity than PD-derived biochar. The fermentation improves the pyrolysis performance. The fermentation enhances adsorption capacity due to unique structure of biochar., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

In this study, pyrolysis kinetics and thermodynamic parameters of Safflower residues (SR) obtained from oil extraction were investigated by using TG/DSC-FTIR and py-GC/MS. Thermal analysis was performed from ambient temperature to 750 °C under a nitrogen atmosphere. The first-order reaction kinetics model was applied to thermal analysis data to determine apparent kinetic parameters. Activation energy and pre-exponential factor were calculated as 76.60 kJ.mol -1 and 1.89x10 6 min -1 , respectively. The thermodynamic parameters such as the change in Gibb's free energy, the difference in enthalpy and the entropy change were calculated to be 201.36 kJ mol -1 , 71.79 kJ mol -1 , and -0.196 kJ mol -1 , respectively. TG/FTIR analysis revealed that CO 2 , C 6 H 5 OH, and CC functional group as the main pyrolysis gas products. According to Py-GC/MS results of SR, the presence of high energy-containing compounds among the pyrolysis products was proved. All these results show that SR is suitable for pyrolysis to produce biofuel and/or chemicals., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In this study, cucumber peel (CP) was treated with Calcium Hydroxide i.e. Ca(OH)2 and its thermal behavior was examined. The pre‐treated cucumber peel (PTCP) was thermally degraded mainly through three steps; first, moisture and light volatile compounds loss (30–132°C); second, primary devolatilization (132 to 337°C) involving intense degradation with mainly re‐formation process and third and final, secondary reactions (337 to 800°C). Lower PTCP activation energy (192.77–183.33 KJ/mol) reflects its easy thermal conversion initiation. The non‐condensable compounds (CO2 & CH4) and condensable products (H2O, CH3CH2OH, CH3COOH, C=C, C6H5OH, HCOOH) were found as 29.75% and 70.25% respectively determined by TG‐FTIR analysis. While, with temperature, relative concentration of condensable compounds decrease significantly and found as 61.38% and 42.5% at lower and higher temperature respectively. By Py/GC–MS analysis, presence of the high energy optimizing compounds and valuable chemicals, i.e. toluene (5.12%), benzene (4.31%) and phenols (27.38%) was confirmed. All these datasets shows that pre‐treatment of CP with Ca(OH)2 might be suitable approach to produce Bioenergy and Bio‐chemicals. [ABSTRACT FROM AUTHOR]

Pyrolysis, a promising method for extracting energy and value-added chemicals from municipal solid waste (MSW), encounters challenges associated with generation of inferior quality oil and low-quality char byproducts. In this context, this study proposed catalytic reforming of pyrolysis volatiles derived from MSW, using MSW char (MSWC) and modified MSWC-based catalysts to produce high-quality oil containing monocyclic aromatic hydrocarbons (MAH), alkanes and alkenes, and H 2 -rich gas products. Three groups of modified MSWC-based catalysts are prepared through the activation of MSWC with Na 2 CO 3 , Zn(NO 3) 2 ⋅6 H 2 O and ZnCl 2 for the reforming process. Experimental findings reveal that impregnating MSW with ZnCl 2 , specifically the ZnCl 2 /C-1:1 char from one-step pyrolysis, exhibits the most favorable catalytic performance, with a 47% selectivity of MAH in oil product, yielding > 25 wt% oil at 450 °C and a calorific value of 26.24 MJ/kg. Simultaneously, 44 wt% of MSW is converted into gas products with a 49 v/v% H 2 concentration for ZnCl 2 /C-1:2 catalyst. The Na 2 CO 3 -activated MSWC catalyst corresponds to the highest oil yields and achieves an alkane selectivity of 45.95 area% in the oil product, while Zn(NO 3) 2 -activated MSWC catalyst corresponds to the highest oxygen compounds in the oil product, thus with the lowest calorific value of 19.4 MJ/kg. These results highlight that varying catalyst modifications to MSW char can effectively improve the production of distinct oil compounds, with Zn[OH]+ species and higher Lewis-acid content in the catalyst exerting a positive influence on aromatic hydrocarbon production; and Na 2 CO 3 facilitating alkane production. This study thus provides valuable insights for upgrading oil product quality and increasing H 2 concentration in gas products, particularly at lower pyrolysis and reforming temperatures. • The effective catalysts for producing hydrocarbon oil contain Lewis-acid. • The ZnCl 2 /C-1:1 catalyst obtained the highest monocyclic aromatic hydrocarbons selectivity of 47%. • Three groups of char-based catalysts all improved H 2 concentration in the gas. • The ZnCl2/C-1:2 catalyst corresponds to H 2 content of 49% in gas product. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Canola oil factory residue was investigated as potential pyrolysis feedstock. • Residue has higher volatile matter, lower moisture content than other biomasses. • Distributed activation energy model applied to canola residue pyrolysis. • Evolved gas analysis showed CO 2 emission increased with temperature. • Thermodynamic and kinetics analysis suggested pyrolysis optimized ∼450 °C. Abstract The identification of biomasses for pyrolytic conversion to biofuels depends on many factors, including: moisture content, elemental and volatile matter composition, thermo-kinetic parameters, and evolved gases. The present work illustrates how canola residue may be a suitable biofuel feedstock for low-temperature (<450 °C) slow pyrolysis with energetically favorable conversions of up to 70 wt% of volatile matter. Beyond this point, thermo-kinetic parameters and activation energies, which increase from 154.3 to 400 kJ/mol from 65 to 80% conversion, suggest that the energy required to initiate conversion is thermodynamically unfavorable. This is likely due to its higher elemental carbon content than similar residues, leading to enhanced carbonization rather than devolatilization at higher temperatures. Evolved gas analysis supports limiting pyrolysis temperature; ethanol and methane conversions are maximized below 500 °C with ∼6% water content. Carbon dioxide is the dominant evolved gas beyond this temperature. [ABSTRACT FROM AUTHOR]

Abstract This study illustrated the pyrolysis of banana peel (BP) as a potential waste management solution. Samples were characterized through Fourier transform infrared spectrometry (FTIR), elemental analysis, and high heating value (HHV) calculation. After pyrolysis experiments were performed at different heating rates (10, 20, 30, and 40 °C min−1) by using a thermogravimetric analyzer coupled with FTIR (TG-FTIR), the apparent activation energies were computed with Friedman, Kissinger–Akahira–Sunose (KAS), and Flynn–Wall–Ozawa (FWO) methods, and the evolved gaseous products were analyzed simultaneously. During pyrolysis, BP underwent three devolatilization steps accompanied by the evolution of some major gaseous products, including CO 2 , CH 4 , H 2 O, CH 3 COOH, C C, C 6 H 5 OH, HCOOH, and CH 3 CH 2 OH. Among them, C C, CH 3 COOH, and CO 2 accounted for approximately 71.56% of the total gaseous products. Gas evolution was more significantly influenced by the pyrolysis temperature than by the heating rate. Pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS) analysis confirmed the presence of some high-energy compounds and valuable chemicals containing aromatic, aldehyde, ketone, and other functional groups. In terms of preliminary energy balance, more than 70% of the total energy output was attributed to the liquid pyrolytic products followed by the solid and gaseous products. The energy recovery ratio of BP pyrolysis was superior to that of other fuel feedstocks. This work provided insights into resolving environmental problems associated with BP management by pyrolyzing BP as a potential source of renewable bioenergy. Highlights • Pyrolytic kinetic and gaseous products of banana peel were investigated. • Banana peel showed bioenergy potential in terms of E a , HHV, and Py-GC/MS analysis. • Relative content of gas product was more affected by temperature than heating rate. • Its energy input and output was comparable with other established feedstocks. [ABSTRACT FROM AUTHOR]

[Display omitted] • Furniture waste pyrolysis was studied using TG-FTIR at 10, 20, and 40 °C/min. • Average E a of 173.34 (±1.11) kJ/mol was needed to make the activated complex. • ANN model predicted pyrolysis with an MSE of 0.3694 and an adjusted R2 of 0.9686. • Pyrolysis products contained –OH and –COOH groups and CH 4 , CO 2 , and H 2 O. The thermal conversion of waste furniture boards (WFB) was performed in a coupled TG-FTIR under an inert atmosphere at different heating rates (10, 20, and 40 °C/min). Kinetic analysis was performed on the obtained TG data using model-free methods. The average activation energy (E a) calculated from three different model-free methods viz Friedman, KAS, and OFW was 175.91 (±3.50), 171.41 (±5.01), and 172.70 (±5.06) kJ/mol, respectively. Distribution of activation energy (DAEM) was performed assuming multiple area normalized Gaussian distributions of pseudo-components. Thermodynamic parameters indicate that the conversion of WFB under pyrolytic conditions is endothermic, but favorable. Artificial neural network model was used to predict thermal degradation. Mean square error (MSE) of 0.3694 and adjusted R 2 value of 0.9686 indicate the agreement of experimental and model prediction. WFB pyrolysis produced molecules with –OH and –COOH functional groups, and small gas molecules such as CH 4 , CO 2 , and H 2 O. [ABSTRACT FROM AUTHOR]

[Display omitted] • Mango Peel as a source of bioenergy, bio-based chemicals productions was investigated. • The apparent activation energy was found in range of 88 kJ mol−1 to 304 kJ mol-1. • Evolved gas analysis was performed to examine chemical compounds. • Py/GC-MS was performed to confirm theme of research manuscript. Waste biomass is one of the promising feedstocks for bioenergy generation in present era. The aim of present study is to demonstrate Mango peel as a source of bioenergy, bio-based chemical and phenols productions via pyrolysis, thermodynamics and evolved gas analyses. Therefore, samples were characterized through thermogravimetric analyser, Fourier transform infrared spectrometry (FTIR) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Pyrolysis experiments were carried out at different heating rates i.e. 10, 20 and 30 °Cmin−1 and thermodynamic parameters were calculated using different kinetic models. The apparent activation energy was found in range of 88 kJ mol−1 to 304 kJ mol−1 with all kinetic models. Evolved gaseous analysis was performed though out pyrolysis and between three temperature intervals for qualitative and quantitative analysis of pyrolytic compounds. Similarly, effect of temperature and heating rate on pyrolytic compounds concentrations were also carried out. Release of several chemicals, aromatics compounds and high phenols concentration i.e. 21.01 % via Py/GC-MS confirms its potential for bioenergy, bio-based chemicals productions and anti-oxidant characteristics associated with phenolic compounds. [ABSTRACT FROM AUTHOR]

This research employs a conventional pyrolysis mechanism model to determine the characteristics and kinetics of waste cabbage leave pyrolysis. Further analysis is conducted using the Multi-path Product Generation model to support the findings. The samples were pyrolyzed from ambient temperature to 1073.15 K at heating rates of 20, 30, 40, and 50 K/min. Average activation energies obtained for waste cabbage leave through the Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa, and Starink methods ranged from 102.44 to 319.71 kJ/mol, 105.43–296.83 kJ/mol, and 115.36–366.19 kJ/mol, respectively. The average values across these methods were 183.97, 181.08, and 207.42 kJ/mol, displaying noticeable variation in activation energies depending on the method employed. Additionally, the model demonstrated: (i) pyrolysis attributes in multi-path reactions, (ii) product-generating regime development, and (iii) valuable insights of pyrolysis product yield and composition. The model comprises three primary devolatilization reactions (iChar, iGas, iTar), two tar cracking reactions (tar to char, tar to gas), and one secondary char reaction. The model parameters accurately align with the thermogravimetric curves at varying heating rates, which demonstrate the progression of multiple product pathways. Thus, this model can be effectively utilized for the simulation of multi-path pyrolysis processes. [Display omitted] • The Multi-path Product Generation model demonstrates multi-path pyrolysis processes. • •The pyrolysis details and characterization of waste cabbage leave were revealed. • The MPG effectively predicts the products yeild of waste cabbage leave. • The model could develop industrial applications for producing high-value chemicals. [ABSTRACT FROM AUTHOR]

This study investigated the pyrolysis of hemp residue using kinetic analysis. The thermal degradation of hemp residue occurred in three temperature ranges, and the activation energy (E a) varied between 147.5 kJ/mol and 299.2 kJ/mol depending on the model-free method used. Combined kinetics, statistical approach, was used to calculate the kinetic triplets including the reaction mechanism and pre-exponential factor besides E a. Boosted regression trees (BRT), machine learning approach, was used to predict the E a during the course of conversion at different heating rates. Bio-oil extracted from hemp residues at different temperatures was examined. The oil contained valuable compounds, including phenols, esters, ethers, aromatics, hydrocarbons, organic acids, furans, alkanes, and ketones. The production of hydrocarbons was found to increase at elevated temperatures, indicating their bioenergy potential. However, acids and esters formation decreased at higher temperatures, while aldehydes were produced by the breakdown of a sugar ring. The study provides insights into the potential of hemp residue to be used in the production of value-added products. • Hemp residue was subjected to slow pyrolysis to analyze its thermal degradation. • Degradation occurred in three temperature ranges, leading to a complex reaction mechanism. • BRT model accurately predicted activation energy at different heating rates. • Bio-oil contains valuable compounds like phenols, hydrocarbons, and D -limonene [ABSTRACT FROM AUTHOR]

• Jerusalem artichoke produces 18–28 tons of waste foliage per hectare. • This waste was subjected to pyrolysis to evaluate its bioenergy potential. • The TGA data were analyzed to elucidate the pyrolytic behavior through kinetic and thermodynamic parameters. • The pyrolytic products were identified using FTIR and GC–MS. • A substantial potential of this waste to produce energy and chemicals is demonstrated. The Jerusalem artichoke (Helianthus tuberosus) is a perennial plant which is adapted to wide climatic conditions ranging from temperate to semiarid regions. Its tubers are alternative to potatoes and it can typically produce 18–28 tons of waste foliage from one hectare which can be exploited for bioenergy via pyrolysis. However, the pyrolytic behavior of its waste was never studied. The present study was focused to assess its potential via pyrolysis, kinetics, thermodynamics, and TG-FTIR-MS based study to produce energy and chemicals. The biomass was subjected to thermal degradation at five heating rates (10, 20, 30, 40, 80 °C/min) under an inert environment. The thermograms showed that the highest rate of thermal transformation was achieved at 270–430 °C. The data were subjected to kinetics and thermodynamics analyses using Kissinger-Akahira-Sunose (KAS), Flynn-Wall-Ozawa (FWO), Starink and Vyazovkin models. The activation energy (E a) and pre-exponential factors remained consistent and ranged from 160 to 175 kJ/mol and 1012–1014 s−1 at conversion fractions ranging from α = 0.2 to α = 0.6. The kinetic parameters showed higher statistical confidence with R2 ≥ 0.98 and good agreement among the data obtained through various models. The high heating value (HHV = 18.76 MJ/kg), change in enthalpy (∼ΔH = 150–170 kJ/mol), and Gibbs free energy (ΔG = 158–168 kJ/mol) demonstrated the substantial bioenergy potential of this waste. Moreover, the pyrolytic gases were subjected to Thermogravimetric-Fourier Transformed Infrared Spectroscopy-Mass Spectrometry (TG-FTIR-MS) analyses to identify the nature of products. The detected functional groups showed that the evolved gases contained aldehydes, phenols, carboxylic acids, esters, aromatic hydrocarbons and methane which indicated the substantial potential of this waste to produce energy and chemicals via pyrolysis causing no competition with the food/feed or land for food/feed. [ABSTRACT FROM AUTHOR]