Pub Date : 2024-10-01DOI: 10.1016/j.jaap.2024.106824
Wenxuan Wu , Felix Wiesner , Juan P. Hidalgo , Jeffrey J. Morrell , Luis Yermán
Chromated copper arsenate (CCA) is a preservative treatment that enhances the biodegradation resistance of wood, essential for prolonging the service life of exterior infrastructure. However, the susceptibility of CCA-treated wood to smouldering combustion presents a significant challenge, as the metals present in the CCA catalyze the smouldering. In this work, we examined the oxidative behaviour of char produced from CCA-treated wood through dynamic thermogravimetric analysis. There was a gradual decrease in the catalytic activity of the CCA as temperature increased, particularly above 400 °C. At this stage, lignin undergoes secondary pyrolysis, and thermal decomposition of CCA complexes occurs. The thermal decomposition of CCA-treated wood at temperatures above 650 °C was similar to that of untreated wood, indicating the possible deactivation of the CCA. The agglomeration of species containing Cu or Cr above 650 °C might be responsible for the deactivation. This process is influenced by simultaneous lignin pyrolysis and decomposition of CCA complexes, which are also likely contributors to the loss of CCA's catalytic activity. This research introduced a novel experimental approach to assess the catalytic effects of CCA on char oxidation at elevated temperatures, offering valuable insights into CCA deactivation and its implications for fire safety. It also contributes to the development of potential modifications to CCA formulations aimed to reduce smouldering in wildfire-prone regions.
铬化砷酸铜（CCA）是一种防腐处理剂，可增强木材的抗生物降解能力，对延长外部基础设施的使用寿命至关重要。然而，由于铬化砷酸铜中的金属会催化烟熏燃烧，因此铬化砷酸铜处理过的木材易受烟熏燃烧的影响，这给我们带来了巨大的挑战。在这项工作中，我们通过动态热重分析研究了经铬化砷酸铜处理的木材产生的炭的氧化行为。随着温度的升高，CCA 的催化活性逐渐降低，尤其是在 400 °C 以上。在此阶段，木质素发生二次热解，CCA 复合物发生热分解。CCA 处理过的木材在 650 °C 以上的热分解与未处理过的木材相似，表明 CCA 可能失活。温度高于 650 °C 时，含铜或铬的物种聚集可能是导致失活的原因。这一过程同时受到木质素热解和 CCA 复合物分解的影响，这也可能是导致 CCA 失去催化活性的原因。这项研究采用了一种新颖的实验方法来评估 CCA 在高温下对木炭氧化的催化作用，为深入了解 CCA 失活及其对消防安全的影响提供了宝贵的资料。它还有助于开发对 CCA 配方的潜在改良，以减少野火易发地区的烟熏现象。
{"title":"Deactivation of chromated copper arsenate as a catalyst in smouldering of wood","authors":"Wenxuan Wu , Felix Wiesner , Juan P. Hidalgo , Jeffrey J. Morrell , Luis Yermán","doi":"10.1016/j.jaap.2024.106824","DOIUrl":"10.1016/j.jaap.2024.106824","url":null,"abstract":"<div><div>Chromated copper arsenate (CCA) is a preservative treatment that enhances the biodegradation resistance of wood, essential for prolonging the service life of exterior infrastructure. However, the susceptibility of CCA-treated wood to smouldering combustion presents a significant challenge, as the metals present in the CCA catalyze the smouldering. In this work, we examined the oxidative behaviour of char produced from CCA-treated wood through dynamic thermogravimetric analysis. There was a gradual decrease in the catalytic activity of the CCA as temperature increased, particularly above 400 °C. At this stage, lignin undergoes secondary pyrolysis, and thermal decomposition of CCA complexes occurs. The thermal decomposition of CCA-treated wood at temperatures above 650 °C was similar to that of untreated wood, indicating the possible deactivation of the CCA. The agglomeration of species containing Cu or Cr above 650 °C might be responsible for the deactivation. This process is influenced by simultaneous lignin pyrolysis and decomposition of CCA complexes, which are also likely contributors to the loss of CCA's catalytic activity. This research introduced a novel experimental approach to assess the catalytic effects of CCA on char oxidation at elevated temperatures, offering valuable insights into CCA deactivation and its implications for fire safety. It also contributes to the development of potential modifications to CCA formulations aimed to reduce smouldering in wildfire-prone regions.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106824"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142535667","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.1016/j.jaap.2024.106806
Meng Yang Tee , Kok Sin Woon , Syie Luing Wong , Bemgba Bevan Nyakuma , Jian Ping Tan , William Woei Fong Chong , Guo Ren Mong
As the rates of population growth and urbanization increase, solid waste management becomes a global challenge, leading to increased research on co-pyrolysis as a sustainable waste management approach. The studies typically begin with thermogravimetric characteristics and kinetic parameter investigations of various feedstock blends. However, a comprehensive examination of the research landscape and future directions of co-pyrolysis kinetics remains lacking in the literature. Therefore, a bibliometric analysis of 461 Web of Science-indexed publications was conducted to examine topical developments from 2001 to 2022. The topic experienced rapid growth in terms of total publications and citations. Bioresource Technology is the most productive journal, while Energy Conversion and Management is the most influential. Due to extensive policy frameworks and financial support, China has made the most significant impact on the co-pyrolysis kinetics field. South China University of Technology is the most prolific organization due to Ma Xiaoqian and other productive authors’ efforts. Keyword analysis revealed that co-pyrolysis kinetics research mainly emphasizes investigations on thermal decomposition behaviour, chemical kinetics, bio-product characteristics, and synergistic relationships within feedstock blends. Literature review revealed that co-pyrolysis applications of biomass–plastics and biomass–sludge feedstock blends have received notable attention from researchers. However, blending sludge and plastic wastes still requires further exploration despite its potential. Furthermore, the upscaling of co-pyrolysis experiments relies on thermogravimetric and kinetic analyses for optimal feedstock combination and operating conditions, ensuring maximum synergy and desired bio-products. Overall, the study offers crucial insights for co-pyrolysis industry players, potentially solidifying its role in global waste valorisation roadmaps.
随着人口增长和城市化进程的加快，固体废物管理已成为一项全球性挑战，因此有关共热解作为一种可持续废物管理方法的研究日益增多。研究通常从各种原料混合物的热重特性和动力学参数调查开始。然而，文献中仍然缺乏对共热解动力学的研究现状和未来方向的全面考察。因此，我们对 461 篇 Web of Science 索引出版物进行了文献计量分析，以研究 2001 年至 2022 年期间的专题发展情况。该主题在出版物总数和引用次数方面都经历了快速增长。生物资源技术》是产量最高的期刊，而《能源转换与管理》则是影响力最大的期刊。由于广泛的政策框架和资金支持，中国在共热解动力学领域的影响最为显著。在马晓倩和其他高产作者的努力下，华南理工大学是最多产的机构。关键词分析表明，共热解动力学研究主要集中在热分解行为、化学动力学、生物产品特性以及原料混合物的协同关系等方面。文献综述显示，生物质-塑料和生物质-污泥原料混合物的共热解应用受到了研究人员的广泛关注。然而，尽管污泥和塑料废弃物混合具有潜力，但仍需进一步探索。此外，共热解实验的升级依赖于热重分析和动力学分析，以获得最佳的原料组合和操作条件，从而确保最大的协同效应和理想的生物产品。总之，该研究为共热解行业参与者提供了重要的见解，有可能巩固其在全球废物价值化路线图中的作用。
{"title":"Unveiling the dynamics of solid waste co-pyrolysis through thermogravimetric analysis and kinetic analysis for technological upscaling (2001–2022)","authors":"Meng Yang Tee , Kok Sin Woon , Syie Luing Wong , Bemgba Bevan Nyakuma , Jian Ping Tan , William Woei Fong Chong , Guo Ren Mong","doi":"10.1016/j.jaap.2024.106806","DOIUrl":"10.1016/j.jaap.2024.106806","url":null,"abstract":"<div><div>As the rates of population growth and urbanization increase, solid waste management becomes a global challenge, leading to increased research on co-pyrolysis as a sustainable waste management approach. The studies typically begin with thermogravimetric characteristics and kinetic parameter investigations of various feedstock blends. However, a comprehensive examination of the research landscape and future directions of co-pyrolysis kinetics remains lacking in the literature. Therefore, a bibliometric analysis of 461 Web of Science-indexed publications was conducted to examine topical developments from 2001 to 2022. The topic experienced rapid growth in terms of total publications and citations. <em>Bioresource Technology</em> is the most productive journal, while <em>Energy Conversion and Management</em> is the most influential. Due to extensive policy frameworks and financial support, China has made the most significant impact on the co-pyrolysis kinetics field. South China University of Technology is the most prolific organization due to <em>Ma Xiaoqian</em> and other productive authors’ efforts. Keyword analysis revealed that co-pyrolysis kinetics research mainly emphasizes investigations on thermal decomposition behaviour, chemical kinetics, bio-product characteristics, and synergistic relationships within feedstock blends. Literature review revealed that co-pyrolysis applications of biomass–plastics and biomass–sludge feedstock blends have received notable attention from researchers. However, blending sludge and plastic wastes still requires further exploration despite its potential. Furthermore, the upscaling of co-pyrolysis experiments relies on thermogravimetric and kinetic analyses for optimal feedstock combination and operating conditions, ensuring maximum synergy and desired bio-products. Overall, the study offers crucial insights for co-pyrolysis industry players, potentially solidifying its role in global waste valorisation roadmaps.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106806"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142425654","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 : 2024-10-01DOI: 10.1016/j.jaap.2024.106797
Shabnam Gharibi , Shohreh Fatemi , Farouq S. Mjalli
The pyrolysis of vacuum residue (VR) using polypropylene (PP) under supercritical carbon dioxide (scCO2) conditions represents a novel approach to converting this abundant and difficult-to-process feedstock into lighter liquid products. In this paper, a set of experiments was performed to analyze the impact of scCO2, PP and steam on the yields of pyrolysis products (i.e., liquid, gas and coke) and characteristics of the liquid fractions. The findings indicated notable improvements when scCO2 was used instead of subcritical CO2 in the pyrolysis of VR with PP. These included decreased viscosity and improved API gravity, alongside increased maltene yield and reduced coke yield. Furthermore, the inclusion of PP markedly elevated the quality of the obtained liquid, whereas steam + scCO2 primarily affected the product distribution by raising the yield of coke and gas fractions. VR pyrolysis under scCO2 conditions at 380 °C, 8 MPa, PP/VR ratio of 0.23 for 60 min in a batch system, without the use of catalyst, resulted in the highest liquid yield of 83.7 ± 1.9 wt%, and minimum coke yield of 9.8 ± 1.3 wt%. Under these conditions, the upgraded liquid consisted of 75.2 wt% light and middle distillates with boiling points below 350 °C. Additionally, the proportion of oxygenates in the pyrolysis oil reduced by 60.5 %, improving its heating value. Moreover, adding PP to the upgrading process resulted in a higher proportion of isoparaffins, cycloparaffins, and aromatics, coupled with a decrease in olefins, aligning the liquid specifications more closely with fuel standards.
{"title":"Upgrading vacuum residue in a supercritical CO2 environment with polypropylene and steam: Insights into products distribution and characterization of liquid products","authors":"Shabnam Gharibi , Shohreh Fatemi , Farouq S. Mjalli","doi":"10.1016/j.jaap.2024.106797","DOIUrl":"10.1016/j.jaap.2024.106797","url":null,"abstract":"<div><div>The pyrolysis of vacuum residue (VR) using polypropylene (PP) under supercritical carbon dioxide (scCO<sub>2</sub>) conditions represents a novel approach to converting this abundant and difficult-to-process feedstock into lighter liquid products. In this paper, a set of experiments was performed to analyze the impact of scCO<sub>2</sub>, PP and steam on the yields of pyrolysis products (i.e., liquid, gas and coke) and characteristics of the liquid fractions. The findings indicated notable improvements when scCO<sub>2</sub> was used instead of subcritical CO<sub>2</sub> in the pyrolysis of VR with PP. These included decreased viscosity and improved API gravity, alongside increased maltene yield and reduced coke yield. Furthermore, the inclusion of PP markedly elevated the quality of the obtained liquid, whereas steam + scCO<sub>2</sub> primarily affected the product distribution by raising the yield of coke and gas fractions. VR pyrolysis under scCO<sub>2</sub> conditions at 380 °C, 8 MPa, PP/VR ratio of 0.23 for 60 min in a batch system, without the use of catalyst, resulted in the highest liquid yield of 83.7 ± 1.9 wt%, and minimum coke yield of 9.8 ± 1.3 wt%. Under these conditions, the upgraded liquid consisted of 75.2 wt% light and middle distillates with boiling points below 350 °C. Additionally, the proportion of oxygenates in the pyrolysis oil reduced by 60.5 %, improving its heating value. Moreover, adding PP to the upgrading process resulted in a higher proportion of isoparaffins, cycloparaffins, and aromatics, coupled with a decrease in olefins, aligning the liquid specifications more closely with fuel standards.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106797"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142425735","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 : 2024-10-01DOI: 10.1016/j.jaap.2024.106820
Lillian N. Tran , Michael Lum , Linhui Tian , Jinyong Liu , Ying-Hsuan Lin
Thermal treatment is a widely used remediation strategy for PFAS-contaminated materials such as soil, spent sorbents, and domestic waste. To better understand the effectiveness and environmental impact of thermal treatments for PFAS-contaminated materials, a fundamental understanding of PFAS thermal degradation mechanisms is required. This work aims to study the pyrolysis of six representative PFAS compounds, all of which have an eight-carbon length but with different functional groups. To assess the thermal stability and pyrolysis products of these six PFAS compounds, evolved gas analysis (EGA) was performed using thermogravimetric analysis/differential scanning calorimetry (TGA/DSC) coupled with an infrared spectrometer (IR) and a mass spectrometer (MS), as well as pyrolysis-GCMS (Pyr-GCMS). The EGA data demonstrates that compounds with lower estimated vapor pressures were generally found to be more thermally labile, and the presence of an ionic bond necessitates higher temperatures for pyrolysis. Pyrolysis at 900 °C yielded a variety of fluorinated organic compounds at significant signals. Tetrafluoroethene constituted the majority of the Pyr-GCMS signal for all the compounds. Moreover, a significant fraction of detected products was unable to be identified, underscoring a need for better tools to help with the identification of unknowns. Pyrolysis can occur through random chain scission, scission of the functional group, scission of the terminal CF3 group, and HF elimination. Some compounds may undergo more complete beta-scission to produce smaller pyrolysis products compared to others. The presence of acidic protons within the functional group can help facilitate HF elimination, whereas the salt form of a PFAS compound is less likely to undergo HF elimination. Termination of radical intermediates can either be recombination with a CF3 radical or hydrogen abstraction (H-abstraction). Observed hydrogen-substituted products indicate that functional groups with higher hydrocarbon character may lead to more H-abstraction terminated products. Overall findings show that the functional group of a PFAS may decrease or increase its thermal stability and lead to different profiles of pyrolysis products.
{"title":"The influence of functional groups on the pyrolysis of per- and polyfluoroalkyl substances","authors":"Lillian N. Tran , Michael Lum , Linhui Tian , Jinyong Liu , Ying-Hsuan Lin","doi":"10.1016/j.jaap.2024.106820","DOIUrl":"10.1016/j.jaap.2024.106820","url":null,"abstract":"<div><div>Thermal treatment is a widely used remediation strategy for PFAS-contaminated materials such as soil, spent sorbents, and domestic waste. To better understand the effectiveness and environmental impact of thermal treatments for PFAS-contaminated materials, a fundamental understanding of PFAS thermal degradation mechanisms is required. This work aims to study the pyrolysis of six representative PFAS compounds, all of which have an eight-carbon length but with different functional groups. To assess the thermal stability and pyrolysis products of these six PFAS compounds, evolved gas analysis (EGA) was performed using thermogravimetric analysis/differential scanning calorimetry (TGA/DSC) coupled with an infrared spectrometer (IR) and a mass spectrometer (MS), as well as pyrolysis-GCMS (Pyr-GCMS). The EGA data demonstrates that compounds with lower estimated vapor pressures were generally found to be more thermally labile, and the presence of an ionic bond necessitates higher temperatures for pyrolysis. Pyrolysis at 900 °C yielded a variety of fluorinated organic compounds at significant signals. Tetrafluoroethene constituted the majority of the Pyr-GCMS signal for all the compounds. Moreover, a significant fraction of detected products was unable to be identified, underscoring a need for better tools to help with the identification of unknowns. Pyrolysis can occur through random chain scission, scission of the functional group, scission of the terminal CF<sub>3</sub> group, and HF elimination. Some compounds may undergo more complete beta-scission to produce smaller pyrolysis products compared to others. The presence of acidic protons within the functional group can help facilitate HF elimination, whereas the salt form of a PFAS compound is less likely to undergo HF elimination. Termination of radical intermediates can either be recombination with a CF<sub>3</sub> radical or hydrogen abstraction (H-abstraction). Observed hydrogen-substituted products indicate that functional groups with higher hydrocarbon character may lead to more H-abstraction terminated products. Overall findings show that the functional group of a PFAS may decrease or increase its thermal stability and lead to different profiles of pyrolysis products.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106820"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444596","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 : 2024-10-01DOI: 10.1016/j.jaap.2024.106822
Seul Yi Kim , Ajit Dattatray Phule , Jae Hwan Yang , Seung-Chul Park
Hydrogen sulfide (H₂S) poses substantial risks to human safety and infrastructure due to its toxicity and corrosive properties. In this study, we present a novel approach to enhance the selective catalytic oxidation of H₂S by synthesizing a nitrogen-doped mesoporous carbon catalyst (denoted as M/B-X-PZ-T) through pyrolysis at 600–800 °C. Our catalyst, derived from commercial biochar, incorporates melamine as a nitrogen source and employs KCl and ZnCl₂ as porogens via the salt-templating method. The resulting catalyst, M/B-1-PZ-700, exhibits an impressive specific surface area of up to 1269.77 m²/g and a high mesopore ratio, with effective nitrogen doping reaching up to 15.35 at%. Remarkably, M/B-1-PZ-700 demonstrated exceptional performance, achieving 100 % H₂S conversion and 94 % sulfur selectivity at 170 °C, surpassing previous nitrogen-doped carbon catalysts. Furthermore, our optimized catalyst maintained over 95 % H₂S conversion and superior sulfur yield for 36 h, indicating excellent long-term stability. This metal-free catalyst derived from biochar offers a promising, sustainable, and eco-friendly solution for effectively mitigating hazardous H₂S emissions.
{"title":"Improving H2S remediation efficiency through metal-free biochar modification: Nitrogen introduction and mesopore formation","authors":"Seul Yi Kim , Ajit Dattatray Phule , Jae Hwan Yang , Seung-Chul Park","doi":"10.1016/j.jaap.2024.106822","DOIUrl":"10.1016/j.jaap.2024.106822","url":null,"abstract":"<div><div>Hydrogen sulfide (H₂S) poses substantial risks to human safety and infrastructure due to its toxicity and corrosive properties. In this study, we present a novel approach to enhance the selective catalytic oxidation of H₂S by synthesizing a nitrogen-doped mesoporous carbon catalyst (denoted as M/B-X-PZ-T) through pyrolysis at 600–800 °C. Our catalyst, derived from commercial biochar, incorporates melamine as a nitrogen source and employs KCl and ZnCl₂ as porogens via the salt-templating method. The resulting catalyst, M/B-1-PZ-700, exhibits an impressive specific surface area of up to 1269.77 m²/g and a high mesopore ratio, with effective nitrogen doping reaching up to 15.35 at%. Remarkably, M/B-1-PZ-700 demonstrated exceptional performance, achieving 100 % H₂S conversion and 94 % sulfur selectivity at 170 °C, surpassing previous nitrogen-doped carbon catalysts. Furthermore, our optimized catalyst maintained over 95 % H₂S conversion and superior sulfur yield for 36 h, indicating excellent long-term stability. This metal-free catalyst derived from biochar offers a promising, sustainable, and eco-friendly solution for effectively mitigating hazardous H₂S emissions.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106822"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536045","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 : 2024-10-01DOI: 10.1016/j.jaap.2024.106826
Shuang Wang , Huihui Zhang , Chunyan Yu , Yue Liu , Yanju Lu , Lu Li
In this study, Co-Corrin/C catalysts with corrin active skeleton were prepared by pyrolysis under anaerobic conditions using vitamin B12 (VB12) as a precursor and activated carbon with rich mesoporous structure as a carrier. The Co-Corrin/C catalyst was applied to the oxidative cleavage reaction of lignin, showing a 92.74 % breakage of β-O-4 bonds. Density functional theory (DFT) calculations indicate that the low energy gap difference of Co-Corrin/C promotes electron transfer between Co and O. Meanwhile, the pyrrole ring in the corrin structure will be adsorbed and bonded to oxygen, which promotes the generation of large amounts of oxygen free radicals. The Cα-OH bond in the lignin aliphatic chain is oxidized to Cα=O bond under the action of oxygen radicals, which reduces the dissociation energy of the β-O-4 bond and significantly improves the oxidation efficiency. Cycling experiments proved that Co-Corrin/C has good stability.
{"title":"Uniformly dispersed Co-Corrin/C catalysts for the study of β-O-4 bonding activity in lignin","authors":"Shuang Wang , Huihui Zhang , Chunyan Yu , Yue Liu , Yanju Lu , Lu Li","doi":"10.1016/j.jaap.2024.106826","DOIUrl":"10.1016/j.jaap.2024.106826","url":null,"abstract":"<div><div>In this study, Co-Corrin/C catalysts with corrin active skeleton were prepared by pyrolysis under anaerobic conditions using vitamin B12 (VB12) as a precursor and activated carbon with rich mesoporous structure as a carrier. The Co-Corrin/C catalyst was applied to the oxidative cleavage reaction of lignin, showing a 92.74 % breakage of β-O-4 bonds. Density functional theory (DFT) calculations indicate that the low energy gap difference of Co-Corrin/C promotes electron transfer between Co and O. Meanwhile, the pyrrole ring in the corrin structure will be adsorbed and bonded to oxygen, which promotes the generation of large amounts of oxygen free radicals. The C<sub>α</sub>-OH bond in the lignin aliphatic chain is oxidized to C<sub>α</sub>=O bond under the action of oxygen radicals, which reduces the dissociation energy of the β-O-4 bond and significantly improves the oxidation efficiency. Cycling experiments proved that Co-Corrin/C has good stability.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106826"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536057","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 : 2024-10-01DOI: 10.1016/j.jaap.2024.106794
Muhammad Irfan Rajput , Jian Li , Beibei Yan , Guanyi Chen , Yunan Sun , Juan Zhao
The environmental impact of landfill stale garbage (LSG), particularly concerning methane emissions and the depletion of valuable resources, presents a significant challenge to environmental sustainability. This research examines the thermochemical properties of LSG, establishing a foundation for the development of efficient treatment methods focused on energy and resource recovery. The TG-FTIR-MS technique and the modified Coast Redfern model were used to evaluate thermal behaviour, gas emissions, and decomposition during the pyrolysis and combustion processes of LSG, both individually and in blends. The study demonstrates that blended component pyrolysis attains a conversion efficiency of up to 85 %, in contrast to 65 % for individual components. This indicates a synergistic effect that implies catalytic actions, which notably improve the decomposition process and decrease pollutants such as sulphur, fluorine, nitrogen compounds, and hazardous halogens that may generate dioxins and furans during combustion. Analysis indicated that the activation energy necessary for the pyrolysis of individual LSG components exhibited significant variation, with values ranging from 7.6 to 217.3 kJ/mol. The blended components demonstrated an activation energy range of 20–178.5 kJ/mol for pyrolysis and 14.1–167.7 kJ/mol for combustion. This study suggests that pyrolysis of blended LSG components is preferable to combustion, as it offers greater efficiency and reduced pollutant emissions, despite combustion's notable energy yield and volume reduction. Our research indicates significant advancements in conversion efficiency and pollutant reduction, prompting a strong recommendation for pyrolysis as the optimal method for LSG treatment. This method demonstrates a balance between resource recovery and environmental responsibility.
{"title":"Kinetic analysis of landfill stale garbage (LSG) pyrolysis and combustion behaviour using thermogravimetry coupled MS and FTIR technique","authors":"Muhammad Irfan Rajput , Jian Li , Beibei Yan , Guanyi Chen , Yunan Sun , Juan Zhao","doi":"10.1016/j.jaap.2024.106794","DOIUrl":"10.1016/j.jaap.2024.106794","url":null,"abstract":"<div><div>The environmental impact of landfill stale garbage (LSG), particularly concerning methane emissions and the depletion of valuable resources, presents a significant challenge to environmental sustainability. This research examines the thermochemical properties of LSG, establishing a foundation for the development of efficient treatment methods focused on energy and resource recovery. The TG-FTIR-MS technique and the modified Coast Redfern model were used to evaluate thermal behaviour, gas emissions, and decomposition during the pyrolysis and combustion processes of LSG, both individually and in blends. The study demonstrates that blended component pyrolysis attains a conversion efficiency of up to 85 %, in contrast to 65 % for individual components. This indicates a synergistic effect that implies catalytic actions, which notably improve the decomposition process and decrease pollutants such as sulphur, fluorine, nitrogen compounds, and hazardous halogens that may generate dioxins and furans during combustion. Analysis indicated that the activation energy necessary for the pyrolysis of individual LSG components exhibited significant variation, with values ranging from 7.6 to 217.3 kJ/mol. The blended components demonstrated an activation energy range of 20–178.5 kJ/mol for pyrolysis and 14.1–167.7 kJ/mol for combustion. This study suggests that pyrolysis of blended LSG components is preferable to combustion, as it offers greater efficiency and reduced pollutant emissions, despite combustion's notable energy yield and volume reduction. Our research indicates significant advancements in conversion efficiency and pollutant reduction, prompting a strong recommendation for pyrolysis as the optimal method for LSG treatment. This method demonstrates a balance between resource recovery and environmental responsibility.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106794"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142425729","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 : 2024-10-01DOI: 10.1016/j.jaap.2024.106790
Chengzhi Liu , Kunmei Su , Zhenhuan Li
Exploring the thermal stability and decarboxylation pathways of FDCA from a microscopic perspective is crucial for the polymerization of furan-based polyesters. In this study, TG-FTIR-MS technology combined with molecular dynamics simulation (ReaxFF-MD) was employed to investigate the thermal decomposition behavior and decarboxylation mechanisms of FDCA. TG-FTIR-MS analysis revealed that FDCA begins to decompose above 200 °C, with the main products being CO2 and 2-furoic acid. ReaxFF-MD simulations showed that in the early stages of decomposition at 1500 K, the primary gaseous products are CO2 and CO. Additionally, catalyst studies demonstrated that tetrabutyl titanate (TBT) is more suitable than Sb2O3 for PEF polymerization. Direct polycondensation of purified BHEF resulted in samples with a reduced absorbance at 400 nm by 0.32, significantly improving the discoloration issue of PEF.
{"title":"Studies on FDCA pyrolysis by TG-FTIR-MS characterization and ReaxFF-MD simulation","authors":"Chengzhi Liu , Kunmei Su , Zhenhuan Li","doi":"10.1016/j.jaap.2024.106790","DOIUrl":"10.1016/j.jaap.2024.106790","url":null,"abstract":"<div><div>Exploring the thermal stability and decarboxylation pathways of FDCA from a microscopic perspective is crucial for the polymerization of furan-based polyesters. In this study, TG-FTIR-MS technology combined with molecular dynamics simulation (ReaxFF-MD) was employed to investigate the thermal decomposition behavior and decarboxylation mechanisms of FDCA. TG-FTIR-MS analysis revealed that FDCA begins to decompose above 200 °C, with the main products being CO<sub>2</sub> and 2-furoic acid. ReaxFF-MD simulations showed that in the early stages of decomposition at 1500 K, the primary gaseous products are CO<sub>2</sub> and CO. Additionally, catalyst studies demonstrated that tetrabutyl titanate (TBT) is more suitable than Sb<sub>2</sub>O<sub>3</sub> for PEF polymerization. Direct polycondensation of purified BHEF resulted in samples with a reduced absorbance at 400 nm by 0.32, significantly improving the discoloration issue of PEF.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106790"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142425730","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 : 2024-10-01DOI: 10.1016/j.jaap.2024.106810
Taewoo Lee , Sangyoon Lee , Doyeon Lee , Eilhann E. Kwon
Plastic waste is a promising resource for producing liquid fuels that can be integrated into existing hydrocarbon infrastructures. However, the heterogeneous nature of plastic-derived liquid fuels limits direct application in internal combustion engines, necessitating their refinement into a usable form. To address these issues, this study explored the enhancement of combustible gaseous fuels derived from plastic waste, footwear waste, as a viable alternative. This approach involves the introduction of carbon dioxide as a reactive feedstock during the pyrolysis process. Analytical techniques were employed to precisely determine the types and compositions of four polymers present in footwear waste. The compositional matrices of the primary pyrogenic products were also identified. However, incorporating carbon dioxide into pyrolysis leads to its interaction with volatile compounds, converting them into lighter gaseous products, particularly carbon monoxide. The homogeneous reactivity of carbon dioxide was further enhanced by the application of heat and a nickel-based catalyst. The gaseous product yield from catalytic pyrolysis in the presence of carbon dioxide increased proportionally with the test temperature. Specifically, the use of carbon dioxide led to a 1.92-fold increase in gaseous product yield at 700 ˚C, in reference to the results from nitrogen. This study demonstrates a technical advancement in pyrolytic valorisation of footwear waste by incorporating carbon dioxide and provides a detailed investigation into its mechanical role in maximising the production of combustible gaseous fuels.
{"title":"Impact of CO2 on the pyrolysis of mixed polymer wastes into combustible fuel: A case study for footwear waste","authors":"Taewoo Lee , Sangyoon Lee , Doyeon Lee , Eilhann E. Kwon","doi":"10.1016/j.jaap.2024.106810","DOIUrl":"10.1016/j.jaap.2024.106810","url":null,"abstract":"<div><div>Plastic waste is a promising resource for producing liquid fuels that can be integrated into existing hydrocarbon infrastructures. However, the heterogeneous nature of plastic-derived liquid fuels limits direct application in internal combustion engines, necessitating their refinement into a usable form. To address these issues, this study explored the enhancement of combustible gaseous fuels derived from plastic waste, footwear waste, as a viable alternative. This approach involves the introduction of carbon dioxide as a reactive feedstock during the pyrolysis process. Analytical techniques were employed to precisely determine the types and compositions of four polymers present in footwear waste. The compositional matrices of the primary pyrogenic products were also identified. However, incorporating carbon dioxide into pyrolysis leads to its interaction with volatile compounds, converting them into lighter gaseous products, particularly carbon monoxide. The homogeneous reactivity of carbon dioxide was further enhanced by the application of heat and a nickel-based catalyst. The gaseous product yield from catalytic pyrolysis in the presence of carbon dioxide increased proportionally with the test temperature. Specifically, the use of carbon dioxide led to a 1.92-fold increase in gaseous product yield at 700 ˚C, in reference to the results from nitrogen. This study demonstrates a technical advancement in pyrolytic valorisation of footwear waste by incorporating carbon dioxide and provides a detailed investigation into its mechanical role in maximising the production of combustible gaseous fuels.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106810"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444595","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 : 2024-10-01DOI: 10.1016/j.jaap.2024.106821
Miao Yu , Gang Gao , Hui Liang , Miao Liu , Jilun Kang , Xiongfei Xu , Wei Zhang
Organic-rich fine-grained rocks are key carriers of unconventional oil and gas resources, making it crucial to understand their hydrocarbon generation and evolution characteristics. This study examines the fine-grained rocks of the second member of the Lucaogou Formation (P2l2) in the Tiaohu and Malang Sags of the Santanghu Basin, focusing on how different organic matter (OM) backgrounds - primarily green algae and cyanobacteria - affect hydrocarbon generation and crude oil properties. Kinetic analysis and hydrous pyrolysis experiments on shales rich in green algae, cyanobacteria, and their mixtures revealed that green algae - derived OM requires lower activation energy to initiate hydrocarbon generation, results in an earlier oil generation peak, and has a broader oil window. Conversely, cyanobacteria - derived OM needs higher activation energy to start hydrocarbon generation, has a later oil peak, and a more concentrated generation period. These findings led to two models: the "green algae origin - early hydrocarbon generation - early oil peak - broad oil window model" and the "cyanobacteria origin - late hydrocarbon generation - late oil peak - concentrated oil generation model." Correlation analysis showed that aromatic hydrocarbons, resins, and asphaltenes significantly degrade crude oil quality. Hydrous pyrolysis experiments indicated that the heavy component content (aromatic hydrocarbons + resins + asphaltenes) in liquid hydrocarbons follows the order: residual oil > absorbed oil > expelled oil, with content initially increasing and then decreasing with maturity, and the color change of liquid hydrocarbons in dichloromethane reflects heavy component content changes effectively. Calculations of density and viscosity of liquid hydrocarbons, based on heavy component content and crude oil properties, were compared with the longitudinal distribution of crude oil properties in the study area. Results show that the hydrocarbon generation characteristics of green algae and cyanobacteria control crude oil properties, highlighting significant intra-source differentiation in the P2l2 shale and validates the phase separation approach in hydrous pyrolysis experiments. The P2l2 shale, with its high OM content and substantial hydrocarbon generation, holds great potential for shale oil exploration, but both reservoir quality and crude oil property evolution under different OM backgrounds should be considered when selecting favorable areas.
富含有机质的细粒岩是非常规油气资源的重要载体，因此了解其油气生成和演化特征至关重要。本研究考察了三塘湖盆地蕉湖和马栏沙格的卢草沟层第二系（P2l2）细粒岩，重点研究了不同有机质（OM）背景--主要是绿藻和蓝藻--如何影响碳氢化合物的生成和原油性质。对富含绿藻、蓝藻及其混合物的页岩进行的动力学分析和水热解实验表明，绿藻衍生的有机质需要较低的活化能来启动碳氢化合物的生成，导致较早的石油生成峰值，并具有较宽的石油窗口。相反，蓝藻衍生的 OM 需要更高的活化能来启动碳氢化合物的生成，其石油生成峰值更晚，生成期更集中。这些发现产生了两个模型："绿藻起源--早期碳氢化合物生成--早期石油峰值--宽石油窗口模型 "和 "蓝藻起源--晚期碳氢化合物生成--晚期石油峰值--集中石油生成模型"。相关分析表明，芳香烃、树脂和沥青质会显著降低原油质量。含水热解实验表明，液态烃中的重组分（芳香烃+树脂+沥青质）含量依次为：残余油>；吸收油>；排出油，含量最初随成熟度增加而增加，然后随成熟度增加而减少，二氯甲烷中液态烃的颜色变化有效地反映了重组分含量的变化。根据重组分含量和原油性质计算出的液态烃密度和粘度与研究区原油性质的纵向分布进行了比较。结果表明，绿藻和蓝藻的碳氢化合物生成特征控制着原油性质，突出表明了 P2l2 页岩中显著的源内分异，并验证了水合热解实验中的相分离方法。P2l2 页岩具有较高的 OM 含量和大量的碳氢化合物生成，在页岩油勘探方面具有巨大潜力，但在选择有利区域时，应同时考虑储层质量和不同 OM 背景下的原油性质演变。
{"title":"Differential hydrocarbon generation characteristics of organic matter with green algae and cyanobateria origins in the Permain Lucaogou Formation of the Santanghu Basin","authors":"Miao Yu , Gang Gao , Hui Liang , Miao Liu , Jilun Kang , Xiongfei Xu , Wei Zhang","doi":"10.1016/j.jaap.2024.106821","DOIUrl":"10.1016/j.jaap.2024.106821","url":null,"abstract":"<div><div>Organic-rich fine-grained rocks are key carriers of unconventional oil and gas resources, making it crucial to understand their hydrocarbon generation and evolution characteristics. This study examines the fine-grained rocks of the second member of the Lucaogou Formation (P<sub>2</sub>l<sub>2</sub>) in the Tiaohu and Malang Sags of the Santanghu Basin, focusing on how different organic matter (OM) backgrounds - primarily green algae and cyanobacteria - affect hydrocarbon generation and crude oil properties. Kinetic analysis and hydrous pyrolysis experiments on shales rich in green algae, cyanobacteria, and their mixtures revealed that green algae - derived OM requires lower activation energy to initiate hydrocarbon generation, results in an earlier oil generation peak, and has a broader oil window. Conversely, cyanobacteria - derived OM needs higher activation energy to start hydrocarbon generation, has a later oil peak, and a more concentrated generation period. These findings led to two models: the \"green algae origin - early hydrocarbon generation - early oil peak - broad oil window model\" and the \"cyanobacteria origin - late hydrocarbon generation - late oil peak - concentrated oil generation model.\" Correlation analysis showed that aromatic hydrocarbons, resins, and asphaltenes significantly degrade crude oil quality. Hydrous pyrolysis experiments indicated that the heavy component content (aromatic hydrocarbons + resins + asphaltenes) in liquid hydrocarbons follows the order: residual oil > absorbed oil > expelled oil, with content initially increasing and then decreasing with maturity, and the color change of liquid hydrocarbons in dichloromethane reflects heavy component content changes effectively. Calculations of density and viscosity of liquid hydrocarbons, based on heavy component content and crude oil properties, were compared with the longitudinal distribution of crude oil properties in the study area. Results show that the hydrocarbon generation characteristics of green algae and cyanobacteria control crude oil properties, highlighting significant intra-source differentiation in the P<sub>2</sub>l<sub>2</sub> shale and validates the phase separation approach in hydrous pyrolysis experiments. The P<sub>2</sub>l<sub>2</sub> shale, with its high OM content and substantial hydrocarbon generation, holds great potential for shale oil exploration, but both reservoir quality and crude oil property evolution under different OM backgrounds should be considered when selecting favorable areas.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106821"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536046","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号