Pub Date : 2025-04-14DOI: 10.1016/j.jaap.2025.107134
Yali Tan , Fangqiao Pang , Mao Gan , Ying Su , Jinbo Liu , Lihong Huang
Auto-thermal reforming (ATR) process is effective in converting biomass-derived acetic acid (HAc) for hydrogen production, and provides a clean, carbon-neutral approach for green hydrogen supply. However, challenges, such as catalytic deactivation by carbon deposition, sintering of active components, and oxidation, need to be addressed. Therefore, monoclinic wolframite-type Ni/MgWO4 catalysts were prepared by the Pechini method and applied in ATR for H2 production. The results indicated that with doping of Mg species in tungsten oxide, mixed phases of monoclinic wolframite-type m-MgWO4 and tetragonal scheelite-type t-MgWO4 were formed. During the ATR process, t-MgWO4 transformed into the more stable m-MgWO4, and thus the wolframite m-MgWO4 existed as the main phase. The stability of m-MgWO4 structure was beneficial for dispersing active component of Ni0 over the MgWO4 support and restraining aggregation of Ni0 species. Furthermore, this transformation promoted formation of oxygen vacancies and enhancing lattice oxygen mobility for gasification of coke precursors. As a result, the Ni0.80W1.11Mg2.02O6.15±δ catalyst with Ni/m-MgWO4 structure demonstrated high stability and activity during ATR test: the conversion rate of acetic acid and the H2 yield remained stable at 100 % and 2.78 mol-H2/mol-HAc, respectively, while no coking was found.
{"title":"Wolframite MgWO4-derived Ni-based catalysts for auto-thermal reforming of acetic acid with high anti-coking properties","authors":"Yali Tan , Fangqiao Pang , Mao Gan , Ying Su , Jinbo Liu , Lihong Huang","doi":"10.1016/j.jaap.2025.107134","DOIUrl":"10.1016/j.jaap.2025.107134","url":null,"abstract":"<div><div>Auto-thermal reforming (ATR) process is effective in converting biomass-derived acetic acid (HAc) for hydrogen production, and provides a clean, carbon-neutral approach for green hydrogen supply. However, challenges, such as catalytic deactivation by carbon deposition, sintering of active components, and oxidation, need to be addressed. Therefore, monoclinic wolframite-type Ni/MgWO<sub>4</sub> catalysts were prepared by the Pechini method and applied in ATR for H<sub>2</sub> production. The results indicated that with doping of Mg species in tungsten oxide, mixed phases of monoclinic wolframite-type m-MgWO<sub>4</sub> and tetragonal scheelite-type t-MgWO<sub>4</sub> were formed. During the ATR process, t-MgWO<sub>4</sub> transformed into the more stable m-MgWO<sub>4</sub>, and thus the wolframite m-MgWO<sub>4</sub> existed as the main phase. The stability of m-MgWO<sub>4</sub> structure was beneficial for dispersing active component of Ni<sup>0</sup> over the MgWO<sub>4</sub> support and restraining aggregation of Ni<sup>0</sup> species. Furthermore, this transformation promoted formation of oxygen vacancies and enhancing lattice oxygen mobility for gasification of coke precursors. As a result, the Ni<sub>0.80</sub>W<sub>1.11</sub>Mg<sub>2.02</sub>O<sub>6.15±δ</sub> catalyst with Ni/m-MgWO<sub>4</sub> structure demonstrated high stability and activity during ATR test: the conversion rate of acetic acid and the H<sub>2</sub> yield remained stable at 100 % and 2.78 mol-H<sub>2</sub>/mol-HAc, respectively, while no coking was found.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"190 ","pages":"Article 107134"},"PeriodicalIF":5.8,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143838352","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-14DOI: 10.1016/j.jaap.2025.107131
Kaiyue Zheng , Zhijie Gong , Song Hu , Mengchuan Jia , Kai Xu , Jun Xu , Long Jiang , Yi Wang , Sheng Su , Jun Xiang
A deeper deoxygenation and upgrading of biomass could be realized through pressurized pyrolysis, whereas the product properties and reaction pathways from different biomass vary significantly, primarily due to components variations and interactions. This study employed reactive force field molecular dynamics (ReaxFF MD) to elucidate co-pyrolysis mechanisms of biomass three components at microcosmic level. The effects of temperatures and pressure on individual component pyrolysis were initially investigated. Results indicated that pressure significantly impacted the pyrolysis of cellulose and hemicellulose, particularly on cellulose, increasing its char yields at 1400–1800 K. The H2O and CO2 yields under pressure were markedly higher than atmospheric pressure. Moreover, by comparing calculated and simulated values, the influence of component interactions on product characteristics under atmospheric and pressurized conditions was analyzed. Simulation results showed that pressure enhanced component interactions, particularly between cellulose and lignin (C-L) at temperatures above 1700 K, with a maximum deviation of 13.97 % in char yields. The actual C2H2O2 and C3H4O3 yields were notably higher than calculated at 1800–2300 K, especially under pressure. C-L co-pressurized pyrolysis resulted in more -CO and -COOH groups removal as aldehyde and carboxylic acid small molecule volatiles. In contrast, cellulose-hemicellulose (C-H) interaction mainly occurred during volatiles secondary reaction at elevated temperature and pressure. These results are consistent with our existing experimental data. Ultimately, by tracking C, H, and O elements dynamic migration, a crucial “initiator” role of radicals in synergistic reactions was revealed. The work provides theoretical support for producing high-quality biochar via optimizing pressure conditions and components regulation.
{"title":"Investigation of components interaction during pressurized pyrolysis of biomass via ReaxFF MD simulation: Free radicals driven synergistic deoxygenation and polymerization reactions","authors":"Kaiyue Zheng , Zhijie Gong , Song Hu , Mengchuan Jia , Kai Xu , Jun Xu , Long Jiang , Yi Wang , Sheng Su , Jun Xiang","doi":"10.1016/j.jaap.2025.107131","DOIUrl":"10.1016/j.jaap.2025.107131","url":null,"abstract":"<div><div>A deeper deoxygenation and upgrading of biomass could be realized through pressurized pyrolysis, whereas the product properties and reaction pathways from different biomass vary significantly, primarily due to components variations and interactions. This study employed reactive force field molecular dynamics (ReaxFF MD) to elucidate co-pyrolysis mechanisms of biomass three components at microcosmic level. The effects of temperatures and pressure on individual component pyrolysis were initially investigated. Results indicated that pressure significantly impacted the pyrolysis of cellulose and hemicellulose, particularly on cellulose, increasing its char yields at 1400–1800 K. The H<sub>2</sub>O and CO<sub>2</sub> yields under pressure were markedly higher than atmospheric pressure. Moreover, by comparing calculated and simulated values, the influence of component interactions on product characteristics under atmospheric and pressurized conditions was analyzed. Simulation results showed that pressure enhanced component interactions, particularly between cellulose and lignin (C-L) at temperatures above 1700 K, with a maximum deviation of 13.97 % in char yields. The actual C<sub>2</sub>H<sub>2</sub>O<sub>2</sub> and C<sub>3</sub>H<sub>4</sub>O<sub>3</sub> yields were notably higher than calculated at 1800–2300 K, especially under pressure. C-L co-pressurized pyrolysis resulted in more -C<img>O and -COOH groups removal as aldehyde and carboxylic acid small molecule volatiles. In contrast, cellulose-hemicellulose (C-H) interaction mainly occurred during volatiles secondary reaction at elevated temperature and pressure. These results are consistent with our existing experimental data. Ultimately, by tracking C, H, and O elements dynamic migration, a crucial “initiator” role of radicals in synergistic reactions was revealed. The work provides theoretical support for producing high-quality biochar via optimizing pressure conditions and components regulation.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"190 ","pages":"Article 107131"},"PeriodicalIF":5.8,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143830219","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-12DOI: 10.1016/j.jaap.2025.107129
Mahsa Lotfi Marchoubeh , Kaylee Morton , Farnaz Beygi Khosroshahi , Stanislav I. Stoliarov
This study presents the development and validation of a novel analytical method for quantifying methyl methacrylate (MMA) yields generated during the controlled pyrolysis of poly(methyl methacrylate) (PMMA) in a Fire Propagation Apparatus (FPA). Active gas sampling using sorbent tubes, coupled with gas chromatography-mass spectrometry (GC-MS), was employed to selectively capture and analyze MMA. This study developed and validated a robust analytical method with high selectivity, sensitivity, and reproducibility, achieving accurate quantification of MMA yields under fire-like conditions. MMA mass yield values were calculated to range between 86.4 % and 89.4 % with average uncertainties of ± 1.5 %. The study found no significant difference in MMA yields across different heat flux settings (25, 50, and 75 kW/m²). Additionally, no significant variation in MMA yield was observed between cast and extruded PMMA under a heat flux of 75 kW/m². Non-targeted analysis of the pyrolyzates revealed the presence of a variety of compounds, with significant contributions from ester and carboxylic acid groups. The method’s practicality and versatility make it suitable for applications in polymer recycling, fire safety modeling, and air quality monitoring.
{"title":"Application of sorbent tube sampling coupled with GC-MS for quantification of methyl methacrylate monomer yields from pyrolysis of poly(methyl methacrylate)","authors":"Mahsa Lotfi Marchoubeh , Kaylee Morton , Farnaz Beygi Khosroshahi , Stanislav I. Stoliarov","doi":"10.1016/j.jaap.2025.107129","DOIUrl":"10.1016/j.jaap.2025.107129","url":null,"abstract":"<div><div>This study presents the development and validation of a novel analytical method for quantifying methyl methacrylate (MMA) yields generated during the controlled pyrolysis of poly(methyl methacrylate) (PMMA) in a Fire Propagation Apparatus (FPA). Active gas sampling using sorbent tubes, coupled with gas chromatography-mass spectrometry (GC-MS), was employed to selectively capture and analyze MMA. This study developed and validated a robust analytical method with high selectivity, sensitivity, and reproducibility, achieving accurate quantification of MMA yields under fire-like conditions. MMA mass yield values were calculated to range between 86.4 % and 89.4 % with average uncertainties of ± 1.5 %. The study found no significant difference in MMA yields across different heat flux settings (25, 50, and 75 kW/m²). Additionally, no significant variation in MMA yield was observed between cast and extruded PMMA under a heat flux of 75 kW/m². Non-targeted analysis of the pyrolyzates revealed the presence of a variety of compounds, with significant contributions from ester and carboxylic acid groups. The method’s practicality and versatility make it suitable for applications in polymer recycling, fire safety modeling, and air quality monitoring.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"190 ","pages":"Article 107129"},"PeriodicalIF":5.8,"publicationDate":"2025-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-11DOI: 10.1016/j.jaap.2025.107120
Khuda Bukhsh , Changkun Chen , Guoxin Su , Shuai Dong , Lei Li , Shuanghui Deng , Xiaodong Li , Junwu Ma , Xuebin Wang
Torrefaction is a widely recognized thermochemical process for converting biomass into energy-dense biochar with improved combustion properties and enhanced grindability. This research performed a comparative evaluation of biochars obtained under traditional nitrogen (N2) torrefaction and flue gas FG torrefaction to explore the potential applications of biochars. The experimental findings indicated that FG torrefaction achieved a higher reduction in solid yield and HHV improvement, thus leading to a higher energy density. The biochar yield from N2 torrefaction ranged from 98.73 and 68.13 %, whereas FG torrefaction resulted in the yield between 97.35 % and 54.73 %. Additionally, compared to N2 torrefaction, a larger surface area, a higher degree of carbonization, and more stable pyrolysis properties were achieved. The carbonization index ranged from 1.00 to 1.23 under N2 conditions and from 1.01 to 1.32 under FG conditions. The higher HGI value and strong correlation analysis suggested that biochar grindability was strongly linked to torrefaction temperature and carbonaceous properties, irrespective of the torrefaction method. The HGI index ranged from 23 to 48 under FG torrefaction conditions and from 23 to 45 under N2 torrefaction conditions. This study highlights the unique potential of FG torrefaction for biochar production, presenting a sustainable approach to waste management and carbon sequestration.
{"title":"Comparative advantages of biomass-derived biochars via torrefaction under flue gas and nitrogen atmosphere","authors":"Khuda Bukhsh , Changkun Chen , Guoxin Su , Shuai Dong , Lei Li , Shuanghui Deng , Xiaodong Li , Junwu Ma , Xuebin Wang","doi":"10.1016/j.jaap.2025.107120","DOIUrl":"10.1016/j.jaap.2025.107120","url":null,"abstract":"<div><div>Torrefaction is a widely recognized thermochemical process for converting biomass into energy-dense biochar with improved combustion properties and enhanced grindability. This research performed a comparative evaluation of biochars obtained under traditional nitrogen (N<sub>2</sub>) torrefaction and flue gas FG torrefaction to explore the potential applications of biochars. The experimental findings indicated that FG torrefaction achieved a higher reduction in solid yield and HHV improvement, thus leading to a higher energy density. The biochar yield from N<sub>2</sub> torrefaction ranged from 98.73 and 68.13 %, whereas FG torrefaction resulted in the yield between 97.35 % and 54.73 %. Additionally, compared to N<sub>2</sub> torrefaction, a larger surface area, a higher degree of carbonization, and more stable pyrolysis properties were achieved. The carbonization index ranged from 1.00 to 1.23 under N<sub>2</sub> conditions and from 1.01 to 1.32 under FG conditions. The higher HGI value and strong correlation analysis suggested that biochar grindability was strongly linked to torrefaction temperature and carbonaceous properties, irrespective of the torrefaction method. The HGI index ranged from 23 to 48 under FG torrefaction conditions and from 23 to 45 under N<sub>2</sub> torrefaction conditions. This study highlights the unique potential of FG torrefaction for biochar production, presenting a sustainable approach to waste management and carbon sequestration.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"190 ","pages":"Article 107120"},"PeriodicalIF":5.8,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143830417","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-09DOI: 10.1016/j.jaap.2025.107121
Swagat Rajkumar Pantawane , Ashish S. Chaurasia , Jayant D. Ekhe
Optimally loaded SrO (10 %) by weight on H-ZSM-5 for catalytic fixed bed downstream fast pyrolysis of lignin is further investigated. The effect of reaction temperature ranging from 450°C to 750°C on lignin was examined and optimized at 550°C with a nitrogen gas flow of 0.5 liters per minute. Purified lignin to catalyst ratio as 25:5 (wt/wt) afforded a maximum 34.2 wt% bio-oil yield. It is compared with the bio-oil obtained without a catalyst based on percentage yield, product distribution, and quality. The metal oxide showed significant changes in the acidic properties of H-ZSM-5. All original characteristics, respectively, pore volume 0.0836 cm3g−1, surface area 253.039 m2g−1, and pore radius 1.62501 nm of H-ZSM-5 showed a decrease on further increase in metal beyond 10 %. The reaction temperature of pyrolysis over 550°C reduces the yield of bio-oil. ESI-MS of bio-oil obtained using a catalyst indicates an overall shift towards the low molecular weight compounds, decreased PDI, and relatively lesser oligomers studied up to 320 m/z ratio. Base sites of SrO promote the transformation of carboxylic acids into ketones, supporting the loss of oxygen. The role of the acidic site of H-ZSM-5 and base sites of SrO contribute to converting oxygenated compounds to phenols, including esters, acids, alcohols, and phenols hydrocarbons. Typically, hydroxy-acids, hydroxy-esters, etc, showed marked resistance to chemical transformation. In comparison, analysis of pyrolysis gas under optimized conditions shows a 2 % higher hydrogen content by volume. Although under slightly altered conditions, catalyst reuse is demonstrated with a fair response.
{"title":"Unveiling the potential of thermo catalytic fast pyrolysis for the production of higher quantities of bio-oil: Lignin-derived oxygenates","authors":"Swagat Rajkumar Pantawane , Ashish S. Chaurasia , Jayant D. Ekhe","doi":"10.1016/j.jaap.2025.107121","DOIUrl":"10.1016/j.jaap.2025.107121","url":null,"abstract":"<div><div>Optimally loaded SrO (10 %) by weight on H-ZSM-5 for catalytic fixed bed downstream fast pyrolysis of lignin is further investigated. The effect of reaction temperature ranging from 450°C to 750°C on lignin was examined and optimized at 550°C with a nitrogen gas flow of 0.5 liters per minute. Purified lignin to catalyst ratio as 25:5 (wt/wt) afforded a maximum 34.2 wt% bio-oil yield. It is compared with the bio-oil obtained without a catalyst based on percentage yield, product distribution, and quality. The metal oxide showed significant changes in the acidic properties of H-ZSM-5. All original characteristics, respectively, pore volume 0.0836 cm<sup>3</sup>g<sup>−1</sup>, surface area 253.039 m<sup>2</sup>g<sup>−1</sup>, and pore radius 1.62501 nm of H-ZSM-5 showed a decrease on further increase in metal beyond 10 %. The reaction temperature of pyrolysis over 550°C reduces the yield of bio-oil. ESI-MS of bio-oil obtained using a catalyst indicates an overall shift towards the low molecular weight compounds, decreased PDI, and relatively lesser oligomers studied up to 320 <em>m/z</em> ratio. Base sites of SrO promote the transformation of carboxylic acids into ketones, supporting the loss of oxygen. The role of the acidic site of H-ZSM-5 and base sites of SrO contribute to converting oxygenated compounds to phenols, including esters, acids, alcohols, and phenols hydrocarbons. Typically, hydroxy-acids, hydroxy-esters, etc, showed marked resistance to chemical transformation. In comparison, analysis of pyrolysis gas under optimized conditions shows a 2 % higher hydrogen content by volume. Although under slightly altered conditions, catalyst reuse is demonstrated with a fair response.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"190 ","pages":"Article 107121"},"PeriodicalIF":5.8,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143817850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-08DOI: 10.1016/j.jaap.2025.107118
Yu Yan , Chao Liu , Lijuan Sun , Jia Ouyang , Jingyu Xu , Xing Wang , Shiliang Wu , Rui Xiao
In this paper, low-temperature precarbonization (LTPC) was proposed to remove oxygen-containing functional groups within biomass for subsequent pelletization. Influences of atmospheres (N2, dry flue gas, and wet flue gas) and temperatures (210–350 °C) on LTPC product properties were thoroughly explored in a self-made rotary kiln with corn stalk (CS) as the typical feedstock. Results showed that conducted LTPC all caused the mass loss in CS, and increased temperatures reinforced this process. Characterizations revealed that these losses were mainly attributed to the degradation of cellulose and hemicellulose components, which simultaneously resulted in the enhancement of carbon content, fixed carbon proportion, and heating value of LTPC CSs. In addition, radicals in LTPC CSs were also monitored and together with the above characterizations confirmed the role of atmosphere on CS LTPC, with the order of dry flue gas ＞ N2 ＞ wet flue gas. Optimal evaluation criteria were then introduced to select the preferred LTPC condition based on the overall consideration of mass yield, energy yield, and higher heating values of LTPC CSs, which was 270 °C in wet flue gas. This work matched well with the wet flue gas scenario in industry and provided a reference for biomass upgrading for subsequent pelletization.
{"title":"Biomass pellets prepared via low-temperature precarbonization: Biomass properties with flue gas treatment","authors":"Yu Yan , Chao Liu , Lijuan Sun , Jia Ouyang , Jingyu Xu , Xing Wang , Shiliang Wu , Rui Xiao","doi":"10.1016/j.jaap.2025.107118","DOIUrl":"10.1016/j.jaap.2025.107118","url":null,"abstract":"<div><div>In this paper, low-temperature precarbonization (LTPC) was proposed to remove oxygen-containing functional groups within biomass for subsequent pelletization. Influences of atmospheres (N<sub>2</sub>, dry flue gas, and wet flue gas) and temperatures (210–350 °C) on LTPC product properties were thoroughly explored in a self-made rotary kiln with corn stalk (CS) as the typical feedstock. Results showed that conducted LTPC all caused the mass loss in CS, and increased temperatures reinforced this process. Characterizations revealed that these losses were mainly attributed to the degradation of cellulose and hemicellulose components, which simultaneously resulted in the enhancement of carbon content, fixed carbon proportion, and heating value of LTPC CSs. In addition, radicals in LTPC CSs were also monitored and together with the above characterizations confirmed the role of atmosphere on CS LTPC, with the order of dry flue gas ＞ N<sub>2</sub> ＞ wet flue gas. Optimal evaluation criteria were then introduced to select the preferred LTPC condition based on the overall consideration of mass yield, energy yield, and higher heating values of LTPC CSs, which was 270 °C in wet flue gas. This work matched well with the wet flue gas scenario in industry and provided a reference for biomass upgrading for subsequent pelletization.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107118"},"PeriodicalIF":5.8,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143808798","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
C2 hydrocarbons are important raw materials in the chemical industry, and the progress of new production processes deserves attention. In this work, C2 hydrocarbons were produced by liquid phase microwave plasma technology using n-heptane as raw material. Ethylene and acetylene were found to be the main products. By high-speed cameras to study the physical process of plasma formation, it was found that the discharge bubble forming cycle is closely related to microwave power, which in turn affects the flow of C2 hydrocarbons. To support our research findings, optical emission spectroscopy (OES) was used to detect the main types and intensities of radicals, and the gas temperature was estimated. It is found that differences in gas temperature and electron densities caused the changes in the concentration of product, the optimal energy efficiency for C2 hydrocarbons production in this study is 0.53 mmol/kJ. The reaction mechanism during microwave discharge was investigated. This technology provides a value reference for promoting future industrial production of C2 hydrocarbons characterized by high efficiency, environmental sustainability, and low energy consumption.
{"title":"Catalyst-free cracking of n-heptane for production of C2 hydrocarbons by microwave discharge plasma in liquid","authors":"Zhonglin Yu, Bing Sun, Guoxuan Ding, Jinglin Liu, Xiaomei Zhu, Yanbin Xin","doi":"10.1016/j.jaap.2025.107119","DOIUrl":"10.1016/j.jaap.2025.107119","url":null,"abstract":"<div><div>C<sub>2</sub> hydrocarbons are important raw materials in the chemical industry, and the progress of new production processes deserves attention. In this work, C<sub>2</sub> hydrocarbons were produced by liquid phase microwave plasma technology using n-heptane as raw material. Ethylene and acetylene were found to be the main products. By high-speed cameras to study the physical process of plasma formation, it was found that the discharge bubble forming cycle is closely related to microwave power, which in turn affects the flow of C<sub>2</sub> hydrocarbons. To support our research findings, optical emission spectroscopy (OES) was used to detect the main types and intensities of radicals, and the gas temperature was estimated. It is found that differences in gas temperature and electron densities caused the changes in the concentration of product, the optimal energy efficiency for C<sub>2</sub> hydrocarbons production in this study is 0.53 mmol/kJ. The reaction mechanism during microwave discharge was investigated. This technology provides a value reference for promoting future industrial production of C<sub>2</sub> hydrocarbons characterized by high efficiency, environmental sustainability, and low energy consumption.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"190 ","pages":"Article 107119"},"PeriodicalIF":5.8,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143817849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, we introduce a new geochemical proxy based on the Tmax-S parameter presented in Cohen-Sadon et. al., (2022). We discuss Tmax-S applicability using various kerogen types and through thermal maturation experiments. Tmax-S, in analogy to the conventional Tmax (Tmax-HC), is the temperature at maximum organic-sulfur (S) elution during a Rock-Eval® 7S pyrolysis. Tmax-S demonstrates a strong dependency to the sulfide/thiophene bonds ratios. Low (< 400 °C) or high (> 415 °C) Tmax-S values indicate abundancy of thermally labile sulfide cross-linkage or refractory thiophene bonds, respectively. In sedimentary rocks, organic-S bonds distribution depends on how S is incorporated into sedimentary organic molecules (sulfurization) and its alteration during thermal maturation. Various thermally immature samples show a correlation (R2 = 0.70) between Tmax-S to the ratio of reactive Fe to H2S, indicating that reactive Fe availability controlled the sulfurization pathway through inter or intra-molecular S addition. With the organic S/C ratio, Tmax-S in immature rocks distinguish between sulfurization pathways and the overall sulfurization intensity. Therefore, Tmax-S can assess sulfurization contribution to organic matter preservation and improves the reconstruction of paleo-environmental conditions such as reactive Fe availability. During thermal maturation, Tmax-S provides a proxy for organic-S structural variations. Compared to Tmax-HC, Tmax-S has a better resolution, by a factor of six, at the early maturation stage. With the conventional Rock-Eval® proxies, Tmax-S demonstrates the dynamic of S compounds and HC generation along with the organic-S structural rearrangement in the remaining kerogen. Thus, Tmax-S is a rapid, robust and simple proxy for diagenetic and thermal maturation processes of sedimentary organic matter.
{"title":"Tmax-S: A new proxy for the role of sulfur on sedimentary organic matter preservation and thermal maturation","authors":"Hadar Cohen-Sadon , Alon Amrani , Shimon Feinstein , Yoav Oved Rosenberg","doi":"10.1016/j.jaap.2025.107115","DOIUrl":"10.1016/j.jaap.2025.107115","url":null,"abstract":"<div><div>In this study, we introduce a new geochemical proxy based on the Tmax-S parameter presented in Cohen-Sadon et. al., (2022). We discuss Tmax-S applicability using various kerogen types and through thermal maturation experiments. Tmax-S, in analogy to the conventional Tmax (Tmax-HC), is the temperature at maximum organic-sulfur (S) elution during a Rock-Eval® 7S pyrolysis. Tmax-S demonstrates a strong dependency to the sulfide/thiophene bonds ratios. Low (< 400 °C) or high (> 415 °C) Tmax-S values indicate abundancy of thermally labile sulfide cross-linkage or refractory thiophene bonds, respectively. In sedimentary rocks, organic-S bonds distribution depends on how S is incorporated into sedimentary organic molecules (sulfurization) and its alteration during thermal maturation. Various thermally immature samples show a correlation (R<sup>2</sup> = 0.70) between Tmax-S to the ratio of reactive Fe to H<sub>2</sub>S, indicating that reactive Fe availability controlled the sulfurization pathway through inter or intra-molecular S addition. With the organic S/C ratio, Tmax-S in immature rocks distinguish between sulfurization pathways and the overall sulfurization intensity. Therefore, Tmax-S can assess sulfurization contribution to organic matter preservation and improves the reconstruction of paleo-environmental conditions such as reactive Fe availability. During thermal maturation, Tmax-S provides a proxy for organic-S structural variations. Compared to Tmax-HC, Tmax-S has a better resolution, by a factor of six, at the early maturation stage. With the conventional Rock-Eval® proxies, Tmax-S demonstrates the dynamic of S compounds and HC generation along with the organic-S structural rearrangement in the remaining kerogen. Thus, Tmax-S is a rapid, robust and simple proxy for diagenetic and thermal maturation processes of sedimentary organic matter.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"190 ","pages":"Article 107115"},"PeriodicalIF":5.8,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143824354","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, peanut shells are selected as a biomass raw material, and biomass-based hierarchically porous graphitic carbons (PS@FN) are prepared by the synergistic effect of Fe catalysis and KOH activation. The obtained porous graphitic carbon material PS@FN has a large specific surface area of 1664.0 m2 g−1 and a good distribution of large-medium-small pore structure. Simultaneously, there is a notable enhancement in the level of graphitization, accompanied by a 13.8 % decrease in the ID/IG value. In order to investigate the potential of the samples as supercapacitor electrode materials, the porous graphitic carbon materials are tested for electrochemical properties by the related researchers. In the three-electrode system, the specific capacitance of PS@FN can reach 384.9 F g−1 at a current density of 1 A g−1 under the environment of 6 M KOH electrolyte, and remains as 311.3 F g−1 at 10 A g−1, with a capacitance retention rate of 80.87 %. In the two-electrode system, the energy density of PS@FN is 7.5 W h kg−1 at a power density of 625 W kg−1, and is still maintained at 6.9 W h kg−1 at 3125 W kg−1. A capacitance retention of 98.16 % is obtained after 10,000 charge/discharge cycles.
{"title":"Preparation of hierarchically porous graphitic carbon materials from peanut shell via a facile catalytic activation method for supercapacitor applications","authors":"Jiajun Wang, Kaiming Dong, Zhenjie Sun, Lingwei Kong, Biao Tang, Songtao Wu, Xiaoyang Huang, Feiqiang Guo","doi":"10.1016/j.jaap.2025.107110","DOIUrl":"10.1016/j.jaap.2025.107110","url":null,"abstract":"<div><div>In this study, peanut shells are selected as a biomass raw material, and biomass-based hierarchically porous graphitic carbons (PS@FN) are prepared by the synergistic effect of Fe catalysis and KOH activation. The obtained porous graphitic carbon material PS@FN has a large specific surface area of 1664.0 m<sup>2</sup> g<sup>−1</sup> and a good distribution of large-medium-small pore structure. Simultaneously, there is a notable enhancement in the level of graphitization, accompanied by a 13.8 % decrease in the I<sub>D</sub>/I<sub>G</sub> value. In order to investigate the potential of the samples as supercapacitor electrode materials, the porous graphitic carbon materials are tested for electrochemical properties by the related researchers. In the three-electrode system, the specific capacitance of PS@FN can reach 384.9 F g<sup>−1</sup> at a current density of 1 A g<sup>−1</sup> under the environment of 6 M KOH electrolyte, and remains as 311.3 F g<sup>−1</sup> at 10 A g<sup>−1</sup>, with a capacitance retention rate of 80.87 %. In the two-electrode system, the energy density of PS@FN is 7.5 W h kg<sup>−1</sup> at a power density of 625 W kg<sup>−1</sup>, and is still maintained at 6.9 W h kg<sup>−1</sup> at 3125 W kg<sup>−1</sup>. A capacitance retention of 98.16 % is obtained after 10,000 charge/discharge cycles.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107110"},"PeriodicalIF":5.8,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143792297","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Plastic waste remains a pressing environmental issue, with conventional recycling methods falling short in efficiency. Hydrothermal liquefaction (HTL) and hydrothermal gasification (HTG) emerge as innovative approaches, transforming plastics like polyethylene (PE), polypropylene (PP), and mixed municipal waste into valuable outputs such as bio-crude oil and syngas. These processes operate under subcritical water conditions (300–350°C) or supercritical water conditions (400–450°C), offering versatile solutions for waste management. This review synthesizes findings from 250 Scopus-indexed articles spanning 1998–2024, tracing the evolution of research from single-polymer studies to investigations of complex, real-world waste streams. Despite progress, challenges remain, including gaps in understanding reaction kinetics and barriers to industrial scalability. Overcoming these hurdles is essential for embedding hydrothermal technologies within the circular economy, enabling efficient resource recovery and pollution reduction. This article delivers a detailed bibliometric analysis and literature review, underscoring the promise of hydrothermal methods for sustainable plastic waste management.
{"title":"Valorization of plastic waste via hydrothermal liquefaction and hydrothermal gasification: Review and bibliometric analysis","authors":"Alshaimaa Moustafa , Kareem Abdelrahman , Amal Abdelhaleem , Irene Samy Fahim","doi":"10.1016/j.jaap.2025.107112","DOIUrl":"10.1016/j.jaap.2025.107112","url":null,"abstract":"<div><div>Plastic waste remains a pressing environmental issue, with conventional recycling methods falling short in efficiency. Hydrothermal liquefaction (HTL) and hydrothermal gasification (HTG) emerge as innovative approaches, transforming plastics like polyethylene (PE), polypropylene (PP), and mixed municipal waste into valuable outputs such as bio-crude oil and syngas. These processes operate under subcritical water conditions (300–350°C) or supercritical water conditions (400–450°C), offering versatile solutions for waste management. This review synthesizes findings from 250 Scopus-indexed articles spanning 1998–2024, tracing the evolution of research from single-polymer studies to investigations of complex, real-world waste streams. Despite progress, challenges remain, including gaps in understanding reaction kinetics and barriers to industrial scalability. Overcoming these hurdles is essential for embedding hydrothermal technologies within the circular economy, enabling efficient resource recovery and pollution reduction. This article delivers a detailed bibliometric analysis and literature review, underscoring the promise of hydrothermal methods for sustainable plastic waste management.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107112"},"PeriodicalIF":5.8,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783127","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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