Pub Date : 2025-02-20DOI: 10.1016/j.jaap.2025.107054
Junchen Zhu , Qi Li , Hairong Yang , Yue Xie , Hongru Feng , Huabing Liu , Boka Xiang , Kailong Yuan , Cuirong Sun , Yuanjiang Pan
Pyrolysis behavior of sucrose esters (SEs) significantly impacts the aroma and quality of cigarettes. However, there is limited research on SEs and their pyrolysis in Flue-cured tobacco. In this study, nine SEs and their three pyrolysis products, glucose esters (GEs), were identified using LC-MSn, with six esters being reported in Flue-cured tobacco for the first time. The aging and baking processes of tobacco leaves promoted the pyrolysis of most SEs along with the formation of GEs. During long-term storage at 4 ℃, tobacco SE was found to undergo 3-methylvaleryl intramolecular migration from glucose to fructose as well as intermolecular elimination and addition reaction of acetyl groups, greatly enriching the types of tobacco SEs. By comparing different storage temperatures, this acyl migration demonstrated a temperature dependence. Under simulated cigarette smoking conditions via thermal microwave plasma treatment, SE was rapidly degraded into GE intermediates, fatty acids, furfural, and other aroma compounds. These insights advance our understanding of SE pyrolysis and aroma development, and provide potential explanations for the structural diversity of tobacco SEs.
{"title":"Analysis and pyrolysis study of sucrose esters in flue-cured tobacco","authors":"Junchen Zhu , Qi Li , Hairong Yang , Yue Xie , Hongru Feng , Huabing Liu , Boka Xiang , Kailong Yuan , Cuirong Sun , Yuanjiang Pan","doi":"10.1016/j.jaap.2025.107054","DOIUrl":"10.1016/j.jaap.2025.107054","url":null,"abstract":"<div><div>Pyrolysis behavior of sucrose esters (SEs) significantly impacts the aroma and quality of cigarettes. However, there is limited research on SEs and their pyrolysis in Flue-cured tobacco. In this study, nine SEs and their three pyrolysis products, glucose esters (GEs), were identified using LC-MS<sup>n</sup>, with six esters being reported in Flue-cured tobacco for the first time. The aging and baking processes of tobacco leaves promoted the pyrolysis of most SEs along with the formation of GEs. During long-term storage at 4 ℃, tobacco SE was found to undergo 3-methylvaleryl intramolecular migration from glucose to fructose as well as intermolecular elimination and addition reaction of acetyl groups, greatly enriching the types of tobacco SEs. By comparing different storage temperatures, this acyl migration demonstrated a temperature dependence. Under simulated cigarette smoking conditions via thermal microwave plasma treatment, SE was rapidly degraded into GE intermediates, fatty acids, furfural, and other aroma compounds. These insights advance our understanding of SE pyrolysis and aroma development, and provide potential explanations for the structural diversity of tobacco SEs.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107054"},"PeriodicalIF":5.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512269","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 : 2025-02-20DOI: 10.1016/j.jaap.2025.107050
Luis Cutz , Sarvesh Misar , Bernat Font , Majd Al-Naji , Wiebren de Jong
The olive oil industry is an important source of agricultural residues throughout its value chain, ranging from intermediate process slurries to relatively dry content pruning residues. Among them, crude olive pomace (COP) is of particular interest since it is abundant, low cost and can be a promising source for bioenergy. Nevertheless, because COP is phytotoxic and has a high moisture content and low energy density, it represents a challenge to conventional processes that usually require a dry and homogenous material. The main novelty of this study is the use of a transition metal catalyst and a central composite design (CCD) approach to optimize the conversion of COP through hydrothermal liquefaction (HTL) into valuable products. Results show that catalytic HTL is capable of converting up to half of the COP into bio-oil. Higher process temperatures resulted in lower bio-oil yields but larger higher heating value (HHV) and lower N content. The bio-oils produced at higher temperatures also show lower concentration of phenols and regarding biochar, a low inorganic content. Without any further upgrading, COP bio-oils produced by HTL are rich in valuable compounds such as oleic acid, phenolic compounds and ketones that can be used in the polymer industry or as chemical intermediates. The highest bio-oil yield was 51.96 wt% at 330 ºC for 30 min and 7.5 wt% catalyst with a HHV of 22.0 MJ/kg. At those operational conditions, the biochar yield was 16.49 wt% with a HHV of 8.9 MJ/kg. The major minerals found in the biochars (CaO, SiO2 and P2O5) suggests that biochar could be well-suited for use in soil applications or as materials for adsorption, especially the non-catalytic ones. Furthermore, the experimental results acquired from HTL of COP were used to develop a global kinetic model. Using an explicit Runge-Kutta method, the kinetic parameters were calculated. After comparing the global kinetic model with a linear system of ordinary differential equations (ODEs) based on the CCD models, results indicate that this approach is more effective in predicting the yields of HTL products.
{"title":"Hydrothermal liquefaction of Spanish crude olive pomace for biofuel and biochar production","authors":"Luis Cutz , Sarvesh Misar , Bernat Font , Majd Al-Naji , Wiebren de Jong","doi":"10.1016/j.jaap.2025.107050","DOIUrl":"10.1016/j.jaap.2025.107050","url":null,"abstract":"<div><div>The olive oil industry is an important source of agricultural residues throughout its value chain, ranging from intermediate process slurries to relatively dry content pruning residues. Among them, crude olive pomace (COP) is of particular interest since it is abundant, low cost and can be a promising source for bioenergy. Nevertheless, because COP is phytotoxic and has a high moisture content and low energy density, it represents a challenge to conventional processes that usually require a dry and homogenous material. The main novelty of this study is the use of a transition metal catalyst and a central composite design (CCD) approach to optimize the conversion of COP through hydrothermal liquefaction (HTL) into valuable products. Results show that catalytic HTL is capable of converting up to half of the COP into bio-oil. Higher process temperatures resulted in lower bio-oil yields but larger higher heating value (HHV) and lower N content. The bio-oils produced at higher temperatures also show lower concentration of phenols and regarding biochar, a low inorganic content. Without any further upgrading, COP bio-oils produced by HTL are rich in valuable compounds such as oleic acid, phenolic compounds and ketones that can be used in the polymer industry or as chemical intermediates. The highest bio-oil yield was 51.96 wt% at 330 ºC for 30 min and 7.5 wt% catalyst with a HHV of 22.0 MJ/kg. At those operational conditions, the biochar yield was 16.49 wt% with a HHV of 8.9 MJ/kg. The major minerals found in the biochars (CaO, SiO<sub>2</sub> and P<sub>2</sub>O<sub>5</sub>) suggests that biochar could be well-suited for use in soil applications or as materials for adsorption, especially the non-catalytic ones. Furthermore, the experimental results acquired from HTL of COP were used to develop a global kinetic model. Using an explicit Runge-Kutta method, the kinetic parameters were calculated. After comparing the global kinetic model with a linear system of ordinary differential equations (ODEs) based on the CCD models, results indicate that this approach is more effective in predicting the yields of HTL products.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107050"},"PeriodicalIF":5.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143465034","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 : 2025-02-20DOI: 10.1016/j.jaap.2025.107053
Jean Constantino Gomes da Silva , Santiago Arias , José Geraldo A. Pacheco , Fábio Trigo Raya , Gonçalo Amarante Guimarães Pereira , Gustavo Mockaitis
The Agave economic chain generates a significant waste, which has potential for sustainable bioenergy through pyrolysis. However, the diversity and heterogeneity of chemical composition of Agave species may pose challenges. This study investigates the impact of species heterogeneity on the pyrolysis of three Agave species (Agave sisalana, Agave tequilana, and Agave wercklei), aiming to correlate pyrolysis and biomass properties. Solid characterization and Py-GC/MS were used to understand Agave physicochemical characteristics and organic group distribution in volatiles, respectively. A multi-step model and advanced numerical methods were employed for the kinetic study. The physicochemical characteristics showed similar values but a distinct distribution of inorganic compounds, predominantly composed of alkali and alkaline earth metals (6–11 %w.b.), potentially influencing the organic groups’ distribution in the volatiles. High relative areas of aliphatic components (13–28 % at 773 K and 16–36 % at 873 K) and low quantity of acidic groups (<2 %) could be attributed to the catalytic deoxygenation promoted by alkali and alkaline earth metals. These findings are significant for future application of Agave in bio-oil production by pyrolysis, as commercial biomasses often yield a high content of oxygenated and acid groups. For the kinetic study, six decomposition profiles were identified in the pyrolysis, encompassing the decomposition of extractives, saponins, lignocellulose, and oxalate salts. The similarity in profiles resulted in approximately equivalent kinetic parameter values and mechanisms among the species. The average values of Ea ranged from 71 to 324 kJ mol−1, k0 values varied between 107-1022, and the reaction mechanisms included n-order and Avrami-Erofeyev types. The validity of the parameters was verified through curve reconstruction. The inorganic composition was chosen as the parameter related to pyrolysis characteristics, as it was the only parameter that differed significantly among the species. Based on the data, normalization and the proposed model demonstrated satisfactory values of R² (>0.9251), QOF (>94 %), and MSE (<2.73 ×10−3). This underscores the model's potential to describe decomposition profiles solely based on knowledge of inorganic composition, regardless of selected Agave species.
{"title":"Exploring the pyrolysis of Agave species as a novel bioenergy source: Thermo-kinetics, modeling, and product composition insights","authors":"Jean Constantino Gomes da Silva , Santiago Arias , José Geraldo A. Pacheco , Fábio Trigo Raya , Gonçalo Amarante Guimarães Pereira , Gustavo Mockaitis","doi":"10.1016/j.jaap.2025.107053","DOIUrl":"10.1016/j.jaap.2025.107053","url":null,"abstract":"<div><div>The <em>Agave</em> economic chain generates a significant waste, which has potential for sustainable bioenergy through pyrolysis. However, the diversity and heterogeneity of chemical composition of <em>Agave</em> species may pose challenges. This study investigates the impact of species heterogeneity on the pyrolysis of three <em>Agave</em> species (<em>Agave sisalana</em>, <em>Agave tequilana</em>, and <em>Agave wercklei</em>), aiming to correlate pyrolysis and biomass properties. Solid characterization and Py-GC/MS were used to understand <em>Agave</em> physicochemical characteristics and organic group distribution in volatiles, respectively. A multi-step model and advanced numerical methods were employed for the kinetic study. The physicochemical characteristics showed similar values but a distinct distribution of inorganic compounds, predominantly composed of alkali and alkaline earth metals (6–11 %<sub>w.b.</sub>), potentially influencing the organic groups’ distribution in the volatiles. High relative areas of aliphatic components (13–28 % at 773 K and 16–36 % at 873 K) and low quantity of acidic groups (<2 %) could be attributed to the catalytic deoxygenation promoted by alkali and alkaline earth metals. These findings are significant for future application of <em>Agave</em> in bio-oil production by pyrolysis, as commercial biomasses often yield a high content of oxygenated and acid groups. For the kinetic study, six decomposition profiles were identified in the pyrolysis, encompassing the decomposition of extractives, saponins, lignocellulose, and oxalate salts. The similarity in profiles resulted in approximately equivalent kinetic parameter values and mechanisms among the species. The average values of <em>E</em><sub><em>a</em></sub> ranged from 71 to 324 kJ mol<sup>−1</sup>, <em>k</em><sub>0</sub> values varied between 10<sup>7</sup>-10<sup>22</sup>, and the reaction mechanisms included n-order and Avrami-Erofeyev types. The validity of the parameters was verified through curve reconstruction. The inorganic composition was chosen as the parameter related to pyrolysis characteristics, as it was the only parameter that differed significantly among the species. Based on the data, normalization and the proposed model demonstrated satisfactory values of <em>R</em>² (>0.9251), <em>QOF</em> (>94 %), and MSE (<2.73 ×10<sup>−3</sup>). This underscores the model's potential to describe decomposition profiles solely based on knowledge of inorganic composition, regardless of selected <em>Agave</em> species.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107053"},"PeriodicalIF":5.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143465035","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 : 2025-02-20DOI: 10.1016/j.jaap.2025.107055
Jun Dong , Yuanjun Tang , Yangqing Hu , Shifeng Wang , Zhaozhi Zhou , Yuxin Shi , Cunen Liu , Fei Wang
Pyrolysis is a promising approach for treating and recovering solid waste. Herein, we experimentally explored the fast pyrolysis of typical solid waste components, including wood biomass, food waste, and Polyvinyl Chloride (PVC) plastic, using the analytical Pyrolysis Gas Chromatography-Mass Spectrometry (Py GC/MS) technique. The chemical compositions of the volatile organic compounds in pyrolytic tar were detected and compared. The effect of the in-situ addition of calcium oxide (CaO) on the process was also validated. Results showed that different waste components yielded varied pyrolysis products. In-situ CaO addition influenced both the types and relative contents of pyrolysis tar species. The most common products from wood biomass pyrolysis were phenols (24.24 % and 34.87 % without and with CaO addition, respectively) and benzenes (15.77 % and 14.72 % without and with CaO addition, respectively). On the other hand, the most common products from food waste pyrolysis were aldehydes (18.09 % and 3.69 % without and with CaO addition, respectively) and ketones (14.45 % and 33.09 % without and with CaO addition, respectively). The most common products from PVC plastic pyrolysis were benzenes (31.87 % and 28.11 % without and with CaO addition, respectively) and naphthalenes (20.71 % and 25.58 % without and with CaO addition, respectively). During waste pyrolysis, the presence of CaO significantly reduced the formation of acidic compounds, ethers, and aldehydes through decarboxylation and decarbonylation reactions. Regarding the generation of valuable chemicals, the addition of CaO facilitated BTXN synthesis from wood and food waste pyrolytic tar. However, it slightly reduced the relative BTX content from PVC pyrolytic tar. These findings could form the basis for developing resource recovery strategies from solid waste using pyrolysis technology.
{"title":"Effect of CaO addition on fast pyrolysis behavior of solid waste components using Py GC/MS","authors":"Jun Dong , Yuanjun Tang , Yangqing Hu , Shifeng Wang , Zhaozhi Zhou , Yuxin Shi , Cunen Liu , Fei Wang","doi":"10.1016/j.jaap.2025.107055","DOIUrl":"10.1016/j.jaap.2025.107055","url":null,"abstract":"<div><div>Pyrolysis is a promising approach for treating and recovering solid waste. Herein, we experimentally explored the fast pyrolysis of typical solid waste components, including wood biomass, food waste, and Polyvinyl Chloride (PVC) plastic, using the analytical Pyrolysis Gas Chromatography-Mass Spectrometry (Py GC/MS) technique. The chemical compositions of the volatile organic compounds in pyrolytic tar were detected and compared. The effect of the in-situ addition of calcium oxide (CaO) on the process was also validated. Results showed that different waste components yielded varied pyrolysis products. <em>In-situ</em> CaO addition influenced both the types and relative contents of pyrolysis tar species. The most common products from wood biomass pyrolysis were phenols (24.24 % and 34.87 % without and with CaO addition, respectively) and benzenes (15.77 % and 14.72 % without and with CaO addition, respectively). On the other hand, the most common products from food waste pyrolysis were aldehydes (18.09 % and 3.69 % without and with CaO addition, respectively) and ketones (14.45 % and 33.09 % without and with CaO addition, respectively). The most common products from PVC plastic pyrolysis were benzenes (31.87 % and 28.11 % without and with CaO addition, respectively) and naphthalenes (20.71 % and 25.58 % without and with CaO addition, respectively). During waste pyrolysis, the presence of CaO significantly reduced the formation of acidic compounds, ethers, and aldehydes through decarboxylation and decarbonylation reactions. Regarding the generation of valuable chemicals, the addition of CaO facilitated BTXN synthesis from wood and food waste pyrolytic tar. However, it slightly reduced the relative BTX content from PVC pyrolytic tar. These findings could form the basis for developing resource recovery strategies from solid waste using pyrolysis technology.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107055"},"PeriodicalIF":5.8,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143474964","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 : 2025-02-19DOI: 10.1016/j.jaap.2025.107040
Zhoufeng Wang , Xiubo Long , Wenlong Yao , Wenchi Zhang , Jinian Yang
Three BPA-type polyarylates (PARS, PARB and PARF) with the same feeding ratio were synthesized by interfacial polymerization by doping three bisphenol A (BPA) derivative monomers (4,4’-sulfobisphenol (BPS), 2,2-bis(4-hydroxy phenyl)butane (BPB) and 9,9-bis(4-hydroxyphenyl)fluorene (BHPF)). The kinetics of thermal decomposition of polyarylate was studied by three methods and the activation energies of PARS, PARB and PARF were 198.34, 218.12 and 234.96 kJ/mol, respectively. The thermal stability of the three polyarylates followed PARS < PARB < PARF. Fitted by the integral Master-Plots method, the random nucleation was the pyrolysis mechanism of BPA-type polyarylates. Further elucidation of the pyrolysis process was attained through the deployment of thermogravimetric analysis coupled with Fourier transform infrared spectrometry (TG/FTIR) and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). The study suggested that the pyrolysis pathways of polyarylates were significantly influenced by the properties of their backbone groups; specifically, the breaking weaker bonds (e.g., C–S, C–O) facilitated the initial cleavage of molecular chains. This preliminary disruption then catalyzed further decomposition, forming the reactive radicals that subsequently underwent self-association or isomerization, culminating in new compounds. The effect of BPA-derived monomers on the thermal properties and pyrolytic behaviour of polyarylate was clearly demonstrated in this study.
通过掺杂三种双酚 A（BPA）衍生物单体（4,4'-磺基双酚（BPS）、2,2-双（4-羟基苯基）丁烷（BPB）和 9,9-双（4-羟基苯基）芴（BHPF）），采用界面聚合法合成了具有相同投料比的三种双酚 A 型聚芳基酸酯（PARS、PARB 和 PARF）。通过三种方法研究了聚芳酸酯的热分解动力学，PARS、PARB 和 PARF 的活化能分别为 198.34、218.12 和 234.96 kJ/mol。三种聚芳基化合物的热稳定性依次为 PARS、PARB 和 PARF。根据积分主图法拟合，随机成核是双酚 A 型聚芳基酸盐的热解机理。通过热重分析-傅立叶变换红外光谱法（TG/FTIR）和热解-气相色谱-质谱法（Py-GC/MS）进一步阐明了热解过程。研究表明，聚芳酸酯的热解途径受其骨架基团性质的显著影响；具体而言，较弱键（如 C-S、C-O）的断裂促进了分子链的初步裂解。这种初步的破坏催化了进一步的分解，形成了活性自由基，这些自由基随后发生自结合或异构化，最终形成新的化合物。本研究清楚地表明了双酚 A 衍生单体对聚芳酸酯热性能和热解行为的影响。
{"title":"Study on the kinetics and mechanism of thermal decomposition of bisphenol A-type polyarylates","authors":"Zhoufeng Wang , Xiubo Long , Wenlong Yao , Wenchi Zhang , Jinian Yang","doi":"10.1016/j.jaap.2025.107040","DOIUrl":"10.1016/j.jaap.2025.107040","url":null,"abstract":"<div><div>Three BPA-type polyarylates (PARS, PARB and PARF) with the same feeding ratio were synthesized by interfacial polymerization by doping three bisphenol A (BPA) derivative monomers (4,4’-sulfobisphenol (BPS), 2,2-bis(4-hydroxy phenyl)butane (BPB) and 9,9-bis(4-hydroxyphenyl)fluorene (BHPF)). The kinetics of thermal decomposition of polyarylate was studied by three methods and the activation energies of PARS, PARB and PARF were 198.34, 218.12 and 234.96 kJ/mol, respectively. The thermal stability of the three polyarylates followed PARS < PARB < PARF. Fitted by the integral Master-Plots method, the random nucleation was the pyrolysis mechanism of BPA-type polyarylates. Further elucidation of the pyrolysis process was attained through the deployment of thermogravimetric analysis coupled with Fourier transform infrared spectrometry (TG/FTIR) and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS). The study suggested that the pyrolysis pathways of polyarylates were significantly influenced by the properties of their backbone groups; specifically, the breaking weaker bonds (e.g., C–S, C–O) facilitated the initial cleavage of molecular chains. This preliminary disruption then catalyzed further decomposition, forming the reactive radicals that subsequently underwent self-association or isomerization, culminating in new compounds. The effect of BPA-derived monomers on the thermal properties and pyrolytic behaviour of polyarylate was clearly demonstrated in this study.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107040"},"PeriodicalIF":5.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143454628","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}
Reductive catalytic fractionation (RCF) of lignocellulosic biomass produces phenolic-rich lignin oil and carbohydrate pulp, but catalyst separation is usually required for pulp utilization. This study introduces an integrated process combining RCF with microwave-assisted pyrolysis (RCF-MAP), enabling complete biomass valorization without catalyst separation. Using Ni/AC, RCF generates phenolic-rich lignin oil and high-quality carbohydrate pulp. The RCF-derived carbohydrate pulp can be directly subjected to microwave-assisted pyrolysis, producing syngas yields of 49.5 wt% with a high H2 to CO ratio of approximately 1:1, suitable for hydroformylation. The Ni/AC catalyst can be recycled back into the MAP process, preventing deactivation seen in conventional thermal pyrolysis. On-line gas analysis revealed that the microwave environment enhances secondary cracking of liquid products, contributing to the hydrogen formation. Mass flow analysis reveals that birch biomass yields approximately 18.9 wt% of lignin oil, 29.6 wt% of syngas (H2 and CO), 20.1 wt% of bio-oil, and 4.9 wt% of char. This integrated RCF-MAP approach efficiently produces both phenolic chemicals and high-quality syngas, supporting industrial-scale utilization of all biomass fractions.
{"title":"Complete valorization of lignocellulosic biomass through integrated reductive catalytic fractionation and microwave-assisted pyrolysis","authors":"Xu Yang, Jiajun Yu, Mingxun Zeng, Zhicheng Luo, Huiyan Zhang","doi":"10.1016/j.jaap.2025.107049","DOIUrl":"10.1016/j.jaap.2025.107049","url":null,"abstract":"<div><div>Reductive catalytic fractionation (RCF) of lignocellulosic biomass produces phenolic-rich lignin oil and carbohydrate pulp, but catalyst separation is usually required for pulp utilization. This study introduces an integrated process combining RCF with microwave-assisted pyrolysis (RCF-MAP), enabling complete biomass valorization without catalyst separation. Using Ni/AC, RCF generates phenolic-rich lignin oil and high-quality carbohydrate pulp. The RCF-derived carbohydrate pulp can be directly subjected to microwave-assisted pyrolysis, producing syngas yields of 49.5 wt% with a high H<sub>2</sub> to CO ratio of approximately 1:1, suitable for hydroformylation. The Ni/AC catalyst can be recycled back into the MAP process, preventing deactivation seen in conventional thermal pyrolysis. On-line gas analysis revealed that the microwave environment enhances secondary cracking of liquid products, contributing to the hydrogen formation. Mass flow analysis reveals that birch biomass yields approximately 18.9 wt% of lignin oil, 29.6 wt% of syngas (H<sub>2</sub> and CO), 20.1 wt% of bio-oil, and 4.9 wt% of char. This integrated RCF-MAP approach efficiently produces both phenolic chemicals and high-quality syngas, supporting industrial-scale utilization of all biomass fractions.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107049"},"PeriodicalIF":5.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143465036","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 : 2025-02-19DOI: 10.1016/j.jaap.2025.107051
Guangxing Wu , Huan Zhang , Xiuqiang Zhang , Qian Guan , Weiwei Zhang , Jia Lu , Weijuan Lan , Zaifeng Li , Shuhua Yang , Hongying Shi
Intensifying fossil fuel crisis has raised significant attention to the utilization of biomass energy, particularly biomass gasification technology, which is pivotal for its large-scale application. However, the generation of biomass tar during gasification remains a major obstacle. Due to the high carbon content of biomass tar and its compositional and property similarities to coal tar and pitch, this study explores the synthesis of nitrogen-doped biochar by combining urea with biomass tar, and evaluates its potential use as an anode material in sodium-ion batteries. The synthesized material, denoted as NT2–1000 (with a urea-to-biomass tar mass ratio of 2:1 and a carbonization temperature of 1000 °C), exhibited a reversible capacity of 257.49 mAh g−1 at a current density of 25 mA g−1, achieving an initial coulombic efficiency of 59.34 %. After 50 cycles at 50 mA g−1, the capacity almost unchanged. At a higher current density of 1000 mA g−1, the material retained 70.33 % of its initial capacity of over 200 cycles (122.6 mAh g−1), demonstrating excellent rate capability and cycling stability, which is desirable for sodium-ion battery anodes. This research presents a novel method for valorizing carbon from biomass tar, thus promoting the high-value use of waste products generated in energy production processes.
化石燃料危机的加剧使生物质能源的利用备受关注，尤其是生物质气化技术，这对于生物质能源的大规模应用至关重要。然而，气化过程中产生的生物质焦油仍然是一个主要障碍。由于生物质焦油含碳量高，且其成分和性质与煤焦油和沥青相似，本研究探讨了通过将尿素与生物质焦油结合合成掺氮生物炭，并评估了其作为钠离子电池阳极材料的潜在用途。合成的材料被命名为 NT2-1000（尿素与生物质焦油的质量比为 2:1，碳化温度为 1000 °C），在电流密度为 25 mA g-1 时显示出 257.49 mAh g-1 的可逆容量，初始库仑效率为 59.34 %。在 50 mA g-1 下循环 50 次后，容量几乎保持不变。在 1000 mA g-1 的较高电流密度下，该材料在超过 200 次循环（122.6 mAh g-1）后仍保持了 70.33% 的初始容量，显示出卓越的速率能力和循环稳定性，这正是钠离子电池阳极所需要的。这项研究提出了一种生物质焦油碳增值的新方法，从而促进了能源生产过程中产生的废品的高值化利用。
{"title":"Converting biomass tar into N-doped biochar: A promising anode material for enhanced sodium-ion batteries","authors":"Guangxing Wu , Huan Zhang , Xiuqiang Zhang , Qian Guan , Weiwei Zhang , Jia Lu , Weijuan Lan , Zaifeng Li , Shuhua Yang , Hongying Shi","doi":"10.1016/j.jaap.2025.107051","DOIUrl":"10.1016/j.jaap.2025.107051","url":null,"abstract":"<div><div>Intensifying fossil fuel crisis has raised significant attention to the utilization of biomass energy, particularly biomass gasification technology, which is pivotal for its large-scale application. However, the generation of biomass tar during gasification remains a major obstacle. Due to the high carbon content of biomass tar and its compositional and property similarities to coal tar and pitch, this study explores the synthesis of nitrogen-doped biochar by combining urea with biomass tar, and evaluates its potential use as an anode material in sodium-ion batteries. The synthesized material, denoted as NT2–1000 (with a urea-to-biomass tar mass ratio of 2:1 and a carbonization temperature of 1000 °C), exhibited a reversible capacity of 257.49 mAh g<sup>−1</sup> at a current density of 25 mA g<sup>−1</sup>, achieving an initial coulombic efficiency of 59.34 %. After 50 cycles at 50 mA g<sup>−1</sup>, the capacity almost unchanged. At a higher current density of 1000 mA g<sup>−1</sup>, the material retained 70.33 % of its initial capacity of over 200 cycles (122.6 mAh g<sup>−1</sup>), demonstrating excellent rate capability and cycling stability, which is desirable for sodium-ion battery anodes. This research presents a novel method for valorizing carbon from biomass tar, thus promoting the high-value use of waste products generated in energy production processes.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107051"},"PeriodicalIF":5.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143465037","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 : 2025-02-19DOI: 10.1016/j.jaap.2025.107007
Sen Lang, Shouyu Zhang, Jifan Yang, Yi Zhou, Zihang Xu, Xiuyuan Han, Jiantian Huang
Hydrothermal (HT) pretreatment and hydrothermal oxidation (HTO) pretreatment can change the internal chemical components of biomass wastes to effectively promote the diversified utilization of the biomass resource and upgrade the quality of terminal productions. In this paper, cotton stalk (CS) and Fir wood sawdust (FS) were pretreated firstly at 160–260 °C to prepare the biochar pellets and activated carbon respectively. The effect of evolution behavior of the three components in CS/FS during HT/HTO process on the physicochemical properties of biochar pellets and activated carbon is explored. The results indicate that HT and HTO pretreatment are beneficial to the quality of biochar pellets and activated carbon. Compared with HT pretreatment, HTO process can effectively alleviate the pretreatment intensity of the preparation of high-quality biochar pellets and activated carbon. HTO pretreatment can promotes the significantly decompositions of cellulose and hemicellulose and aromatization growth of CS/FS. The biochar pellets with higher physical properties can be prepared at the HT temperature of 230 °C and at the HTO temperature of 200 °C respectively, and the physical properties of the samples prepared from FS basically higher than CS. Crystalline cellulose is the main contributor to the physical property of biochar pellets. The HHV of biochar pellets prepared from pretreated FS is basically higher than CS, and the cellulose is responsible for the increasing HHV. HT and HTO pretreatment can significantly improve the energy density of CS/FS samples, and the apparent density has the crucial effect on the energy density than HHV. The increasing of cellulose content is conductive to the improvement of combustion performance of biochar pellets, while recondensed lignin in FS prepared by HTO process also has the higher HHV and combustion performance. The total yield of resulted samples was affected by the combination of pretreatment yield and activation yield. Compared with the direct activation, the total yield of pretreated CS activated carbon prepared by HT and HTO pretreatment could up to 166.6 % and 118.4 % respectively, and 189.8 % and 118.9 % for FS samples. CS is the more excellent precursor to prepare high-quality activated carbon than FS. Compared with HT pretreatment, the higher specific surface area and adsorption capacity of resulted activated carbon can be obtained by HTO process, in which the iodine adsorption value of CS-HTO180-A and CS-HTO200-A meet the China standard of activated carbon for water purification (GB/T 13803.2–1999).
{"title":"Effect of hydrothermal and hydrothermal oxidation pretreatment on the physicochemical properties of biochar pellet and activated carbon prepared from biomass wastes","authors":"Sen Lang, Shouyu Zhang, Jifan Yang, Yi Zhou, Zihang Xu, Xiuyuan Han, Jiantian Huang","doi":"10.1016/j.jaap.2025.107007","DOIUrl":"10.1016/j.jaap.2025.107007","url":null,"abstract":"<div><div>Hydrothermal (HT) pretreatment and hydrothermal oxidation (HTO) pretreatment can change the internal chemical components of biomass wastes to effectively promote the diversified utilization of the biomass resource and upgrade the quality of terminal productions. In this paper, cotton stalk (CS) and Fir wood sawdust (FS) were pretreated firstly at 160–260 °C to prepare the biochar pellets and activated carbon respectively. The effect of evolution behavior of the three components in CS/FS during HT/HTO process on the physicochemical properties of biochar pellets and activated carbon is explored. The results indicate that HT and HTO pretreatment are beneficial to the quality of biochar pellets and activated carbon. Compared with HT pretreatment, HTO process can effectively alleviate the pretreatment intensity of the preparation of high-quality biochar pellets and activated carbon. HTO pretreatment can promotes the significantly decompositions of cellulose and hemicellulose and aromatization growth of CS/FS. The biochar pellets with higher physical properties can be prepared at the HT temperature of 230 °C and at the HTO temperature of 200 °C respectively, and the physical properties of the samples prepared from FS basically higher than CS. Crystalline cellulose is the main contributor to the physical property of biochar pellets. The HHV of biochar pellets prepared from pretreated FS is basically higher than CS, and the cellulose is responsible for the increasing HHV. HT and HTO pretreatment can significantly improve the energy density of CS/FS samples, and the apparent density has the crucial effect on the energy density than HHV. The increasing of cellulose content is conductive to the improvement of combustion performance of biochar pellets, while recondensed lignin in FS prepared by HTO process also has the higher HHV and combustion performance. The total yield of resulted samples was affected by the combination of pretreatment yield and activation yield. Compared with the direct activation, the total yield of pretreated CS activated carbon prepared by HT and HTO pretreatment could up to 166.6 % and 118.4 % respectively, and 189.8 % and 118.9 % for FS samples. CS is the more excellent precursor to prepare high-quality activated carbon than FS. Compared with HT pretreatment, the higher specific surface area and adsorption capacity of resulted activated carbon can be obtained by HTO process, in which the iodine adsorption value of CS-HTO180-A and CS-HTO200-A meet the China standard of activated carbon for water purification (GB/T 13803.2–1999).</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107007"},"PeriodicalIF":5.8,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143479589","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 : 2025-02-18DOI: 10.1016/j.jaap.2025.107044
Mahendra Tiwari, Ravikrishnan Vinu
Four different biomass feedstocks, viz., rice straw (RS), sugarcane bagasse (BG), pine wood (PW), and Prosopis juliflora (PJ), were pyrolyzed in a microwave reactor at 800 W- 800 °C, and the hydrogen generation potential was assessed under different conditions using Ni/α-Al2O3 catalyst. Uniquely, four different configurations were evaluated in this study, which include non-catalytic pyrolysis of biomass in powder and pellet forms, and catalytic pyrolysis of biomass pellets in in-situ and ex-situ modes. The hydrogen yield was high in the case of biomass pellets and in the presence of catalyst. The general trend was: (biomass pellets) In-situ > (biomass pellets) Ex-situ > biomass pellets > powder biomass. The heating rates also followed the above trend for all biomass feedstocks. Gas yield increased by 2–10 % with pelletization of biomass, and 18–32 % with the use of catalyst due to efficient cracking of the pyrolysis vapours. The H2:CO (mol/mol) ratio was higher in the case of in-situ pyrolysis mode, and the trend was: BG (1.60) > PW (1.52) > RS (1.32) ≈ PJ (1.31). In-situ catalytic pyrolysis of PW pellets yielded high amount of hydrogen (39 vol%, 27.7 g/kgbiomass). In-situ catalytic pyrolysis mode was effective for higher hydrogen yield due to better contact of the pyrolysates with the Ni catalyst that effectively promoted water gas shift reaction. Ex-situ catalytic pyrolysis of biomass pellets produced high yield of CO+CO2. Detailed bio-oil composition analysis revealed that the selectivity to phenolics in the bio-oil obtained from biomass pellets (64–71 %) was more than that from biomass in powder form (51–61 %). Notably, in-situ catalytic pyrolysis of pellets resulted in a sharp decline in phenolic selectivity (22–45 %) accompanied by increased production of aliphatic oxygenates (38–52 %), and mild increase in aliphatic hydrocarbons. This study proves that microwave-assisted pyrolysis of biomass pellets is a promising strategy for hydrogen generation at high yields with good potential to reform the gases for further enhancement of hydrogen.
{"title":"In situ and ex situ catalytic microwave pyrolysis of biomass pellets using Ni/Al2O3 for hydrogen and bio-oil production","authors":"Mahendra Tiwari, Ravikrishnan Vinu","doi":"10.1016/j.jaap.2025.107044","DOIUrl":"10.1016/j.jaap.2025.107044","url":null,"abstract":"<div><div>Four different biomass feedstocks, viz., rice straw (RS), sugarcane bagasse (BG), pine wood (PW), and <em>Prosopis juliflora</em> (PJ), were pyrolyzed in a microwave reactor at 800 W- 800 °C, and the hydrogen generation potential was assessed under different conditions using Ni/α-Al<sub>2</sub>O<sub>3</sub> catalyst. Uniquely, four different configurations were evaluated in this study, which include non-catalytic pyrolysis of biomass in powder and pellet forms, and catalytic pyrolysis of biomass pellets in in-situ and ex-situ modes. The hydrogen yield was high in the case of biomass pellets and in the presence of catalyst. The general trend was: (biomass pellets) <sub>In-situ</sub> > (biomass pellets) <sub>Ex-situ</sub> > biomass pellets > powder biomass. The heating rates also followed the above trend for all biomass feedstocks. Gas yield increased by 2–10 % with pelletization of biomass, and 18–32 % with the use of catalyst due to efficient cracking of the pyrolysis vapours. The H<sub>2</sub>:CO (mol/mol) ratio was higher in the case of in-situ pyrolysis mode, and the trend was: BG (1.60) > PW (1.52) > RS (1.32) ≈ PJ (1.31). In-situ catalytic pyrolysis of PW pellets yielded high amount of hydrogen (39 vol%, 27.7 g/kg<sub>biomass</sub>). In-situ catalytic pyrolysis mode was effective for higher hydrogen yield due to better contact of the pyrolysates with the Ni catalyst that effectively promoted water gas shift reaction. Ex-situ catalytic pyrolysis of biomass pellets produced high yield of CO+CO<sub>2</sub>. Detailed bio-oil composition analysis revealed that the selectivity to phenolics in the bio-oil obtained from biomass pellets (64–71 %) was more than that from biomass in powder form (51–61 %). Notably, in-situ catalytic pyrolysis of pellets resulted in a sharp decline in phenolic selectivity (22–45 %) accompanied by increased production of aliphatic oxygenates (38–52 %), and mild increase in aliphatic hydrocarbons. This study proves that microwave-assisted pyrolysis of biomass pellets is a promising strategy for hydrogen generation at high yields with good potential to reform the gases for further enhancement of hydrogen.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107044"},"PeriodicalIF":5.8,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143526571","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 : 2025-02-18DOI: 10.1016/j.jaap.2025.107042
Xin-xiao Lu , Guo-yu Shi , Guan Wang , Shuo Wang , Rui-nan Zhang , Zi-yao Chen
The water atmosphere exerts a profound effect on the coal pyrolysis process. The present study dissects the bituminous pyrolysis product distribution at 0 %-24 % water content and traces the N and S atom migration via the ReaxFF molecular dynamics (MD). The coal mass ratio exhibits a slow-rapid-slow decline as the temperature rises. The coal mass ratio transfers to the pyrolysis heavy tar, light tar, and gas by 2.65 %, 6.46 %, and 16.51 % at 2700 K. The remaining N and S atoms in char are 62.5 % and 43.3 %, and the migrated atoms mainly distribute in the light tar and gas. The N and S atoms tend to remove from the functional group C4H5N and R-S-R. The elevated temperature promotes the conversion from C-N and C-S to H-N and H-S that contributes to more NH3 and H2S. The minimum char and maximum gas mass arise at the 6 % water content with the lowest total bond number. The heavy and light tar mass peak appears at 12 % and 18 % water content. The active radicals OH∙ and H∙ rise at a higher water content. The research achievement has positive practical significance for the pollution control and efficiency improvement of coal pyrolysis.
{"title":"Water content effect on bituminous pyrolysis product distribution with ReaxFF molecular dynamics and experiment","authors":"Xin-xiao Lu , Guo-yu Shi , Guan Wang , Shuo Wang , Rui-nan Zhang , Zi-yao Chen","doi":"10.1016/j.jaap.2025.107042","DOIUrl":"10.1016/j.jaap.2025.107042","url":null,"abstract":"<div><div>The water atmosphere exerts a profound effect on the coal pyrolysis process. The present study dissects the bituminous pyrolysis product distribution at 0 %-24 % water content and traces the N and S atom migration via the ReaxFF molecular dynamics (MD). The coal mass ratio exhibits a slow-rapid-slow decline as the temperature rises. The coal mass ratio transfers to the pyrolysis heavy tar, light tar, and gas by 2.65 %, 6.46 %, and 16.51 % at 2700 K. The remaining N and S atoms in char are 62.5 % and 43.3 %, and the migrated atoms mainly distribute in the light tar and gas. The N and S atoms tend to remove from the functional group C<sub>4</sub>H<sub>5</sub>N and R-S-R. The elevated temperature promotes the conversion from C-N and C-S to H-N and H-S that contributes to more NH<sub>3</sub> and H<sub>2</sub>S. The minimum char and maximum gas mass arise at the 6 % water content with the lowest total bond number. The heavy and light tar mass peak appears at 12 % and 18 % water content. The active radicals OH∙ and H∙ rise at a higher water content. The research achievement has positive practical significance for the pollution control and efficiency improvement of coal pyrolysis.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"188 ","pages":"Article 107042"},"PeriodicalIF":5.8,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143471373","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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