Journal of Analytical and Applied Pyrolysis最新文献

英文中文

Physicochemical, kinetic, and bond-energy analyses of the pyrolysis of carbon-fiber-reinforced polymer waste

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-01-16 DOI: 10.1016/j.jaap.2025.106972

Lingwen Dai , Xiaomin Hu , Huixin Zhou , Xiaozhen liu , Yuchen Wu , Liru Sun , Xinqian Shu

The increasing demand for carbon-fiber-reinforced polymer (CFRP) is generating large amounts of waste. Although the pyrolysis of CFRP is an effective recycling method to recover carbon fibers, detailed analyses of the pyrolysis mechanism and the effect of the curing agent are lacking. Therefore, this study combines mathematical and physicochemical analyses to investigate the intrinsic mechanism of pyrolysis of CFRP with a bisphenol A epoxy resin matrix and methyl tetrahydro phthalic anhydride as the curing agent. Non-isothermal degradation kinetics and thermal measurements at various heating rates indicated that the dynamic apparent activation energy increases with increasing conversion rate. An optimized pyrolysis reaction model was developed using diffusion as the primary mechanism. The thermodynamic parameters increased during pyrolysis, consistent with the heat demand for the reaction increasing from 151.45 to 318.33 kJ·mol⁻¹. Based on the analysis of the products, energy, and kinetic parameters, thermal degradation in this system was identified in three stages: depolymerization of repeating polymer units below 648 K, release of major organic matter at 648–740 K, and secondary cleavage of organic matter above 740 K. A thermal degradation pathway is proposed based on the calculation of bond dissociation energies and product analysis.

{"title":"Physicochemical, kinetic, and bond-energy analyses of the pyrolysis of carbon-fiber-reinforced polymer waste","authors":"Lingwen Dai , Xiaomin Hu , Huixin Zhou , Xiaozhen liu , Yuchen Wu , Liru Sun , Xinqian Shu","doi":"10.1016/j.jaap.2025.106972","DOIUrl":"10.1016/j.jaap.2025.106972","url":null,"abstract":"<div><div>The increasing demand for carbon-fiber-reinforced polymer (CFRP) is generating large amounts of waste. Although the pyrolysis of CFRP is an effective recycling method to recover carbon fibers, detailed analyses of the pyrolysis mechanism and the effect of the curing agent are lacking. Therefore, this study combines mathematical and physicochemical analyses to investigate the intrinsic mechanism of pyrolysis of CFRP with a bisphenol A epoxy resin matrix and methyl tetrahydro phthalic anhydride as the curing agent. Non-isothermal degradation kinetics and thermal measurements at various heating rates indicated that the dynamic apparent activation energy increases with increasing conversion rate. An optimized pyrolysis reaction model was developed using diffusion as the primary mechanism. The thermodynamic parameters increased during pyrolysis, consistent with the heat demand for the reaction increasing from 151.45 to 318.33 kJ·mol<sup>−1</sup>. Based on the analysis of the products, energy, and kinetic parameters, thermal degradation in this system was identified in three stages: depolymerization of repeating polymer units below 648 K, release of major organic matter at 648–740 K, and secondary cleavage of organic matter above 740 K. A thermal degradation pathway is proposed based on the calculation of bond dissociation energies and product analysis.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106972"},"PeriodicalIF":5.8,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172345","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}

引用次数: 0

Investigation of catalytic hydrothermal co-liquefaction of oil shale and algal biomass

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-01-16 DOI: 10.1016/j.jaap.2025.106974

Jingjing Li , Chuandong Li , Xinjun Ma , Xiaodong Tang , Xianglong Meng , Xiaoli Wang

The hydrothermal co-liquefaction (HTL) conversion process of oil shale and Chlorella was investigated under the catalysis of Ce/HZSM-5 in the experimental study. The results showed that the oil yield and quality were greatly improved after Ce/HZSM-5 was added. At 300°C and a reaction time of 30 minutes, with a Ce loading of 5 % and a Ce/HZSM-5 dosage of 5 wt%, the oil yield was 32.63 %. After adding the catalyst, the relative content of alkanes increased from 7.43 % to 41.63 %, and the content of ketones decreased from 48.18 % to 10.56 %. According to the TG-DSC analysis of the oil, its calorific value is calculated to be 39.8 MJ/kg, which is comparable to that of biodiesel. The calorific value of the oil was increased by 11.1MJ/kg compared with no catalyst. At the same time, the H/C ratio and nitrogen content increased, while the oxygen content decreased by 3.237 %, indicating that Ce/HZSM-5 promoted the hydrodeoxygenation of the oil. Based on the comparison of oil shale before and after the reaction, and the XPS analysis of the catalyst before and after the reaction, the mechanism of the catalytic conversion process was determined. In this mechanism, Ce/HZSM-5 plays a crucial role.

{"title":"Investigation of catalytic hydrothermal co-liquefaction of oil shale and algal biomass","authors":"Jingjing Li , Chuandong Li , Xinjun Ma , Xiaodong Tang , Xianglong Meng , Xiaoli Wang","doi":"10.1016/j.jaap.2025.106974","DOIUrl":"10.1016/j.jaap.2025.106974","url":null,"abstract":"<div><div>The hydrothermal co-liquefaction (HTL) conversion process of oil shale and Chlorella was investigated under the catalysis of Ce/HZSM-5 in the experimental study. The results showed that the oil yield and quality were greatly improved after Ce/HZSM-5 was added. At 300°C and a reaction time of 30 minutes, with a Ce loading of 5 % and a Ce/HZSM-5 dosage of 5 wt%, the oil yield was 32.63 %. After adding the catalyst, the relative content of alkanes increased from 7.43 % to 41.63 %, and the content of ketones decreased from 48.18 % to 10.56 %. According to the TG-DSC analysis of the oil, its calorific value is calculated to be 39.8 MJ/kg, which is comparable to that of biodiesel. The calorific value of the oil was increased by 11.1MJ/kg compared with no catalyst. At the same time, the H/C ratio and nitrogen content increased, while the oxygen content decreased by 3.237 %, indicating that Ce/HZSM-5 promoted the hydrodeoxygenation of the oil. Based on the comparison of oil shale before and after the reaction, and the XPS analysis of the catalyst before and after the reaction, the mechanism of the catalytic conversion process was determined. In this mechanism, Ce/HZSM-5 plays a crucial role.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106974"},"PeriodicalIF":5.8,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172344","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}

引用次数: 0

Insight of the effect of Fe content in Fe/biochar on the conversion of syngas to olefins via Fischer-Tropsch synthesis

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-01-15 DOI: 10.1016/j.jaap.2025.106973

Mingqiang Chen , Quan Wang , Defang Liang , Yishuang Wang , Chang Li , Xuemei Shen , Chunyue cheng , Jun Wang

Herein, a series of Fe-based biochar catalysts (xFe/WSBC) were synthesised via impregnation using wheat straw as a carbon precursor and applied to the Fischer–Tropsch synthesis of olefins (FTO) from syngas. Various characterisations of fresh catalysts demonstrated that Fe content significantly affected the dispersion of iron particles and the surface distribution of Fe^3 +/Fe²⁺. Among the samples, 5Fe/WSBC exhibited the highest surface Fe³⁺/Fe²⁺ ratio and thus the lowest surface electron density, which enhanced the adsorption and activation of H₂. In addition, an appropriate amount of the Fe additive (5 wt%) significantly decreased the Fe₃O₄ particle size, which promoted the continuous reduction and carbonisation processes during FTO to generate iron carbide phases, which boosted CO activation and the subsequent C–C coupling. Therefore, 5Fe/WSBC exhibited the highest CO conversion (46.9 %) and iron time yield (348.9 μmol_CO·g_Fe⁻¹·s⁻¹) as well as the major enhancement of selectivity to light olefins (C₂⁼–C₄⁼). The results for the used catalysts demonstrated that 5 wt% Fe clearly inhibited the sintering of iron particle size and improved the catalytic stability of FTO.

{"title":"Insight of the effect of Fe content in Fe/biochar on the conversion of syngas to olefins via Fischer-Tropsch synthesis","authors":"Mingqiang Chen , Quan Wang , Defang Liang , Yishuang Wang , Chang Li , Xuemei Shen , Chunyue cheng , Jun Wang","doi":"10.1016/j.jaap.2025.106973","DOIUrl":"10.1016/j.jaap.2025.106973","url":null,"abstract":"<div><div>Herein, a series of Fe-based biochar catalysts (xFe/WSBC) were synthesised via impregnation using wheat straw as a carbon precursor and applied to the Fischer–Tropsch synthesis of olefins (FTO) from syngas. Various characterisations of fresh catalysts demonstrated that Fe content significantly affected the dispersion of iron particles and the surface distribution of Fe<sup>3 +</sup>/Fe<sup>2+</sup>. Among the samples, 5Fe/WSBC exhibited the highest surface Fe<sup>3+</sup>/Fe<sup>2+</sup> ratio and thus the lowest surface electron density, which enhanced the adsorption and activation of H<sub>2</sub>. In addition, an appropriate amount of the Fe additive (5 wt%) significantly decreased the Fe<sub>3</sub>O<sub>4</sub> particle size, which promoted the continuous reduction and carbonisation processes during FTO to generate iron carbide phases, which boosted CO activation and the subsequent C–C coupling. Therefore, 5Fe/WSBC exhibited the highest CO conversion (46.9 %) and iron time yield (348.9 μmol<sub>CO</sub>·g<sub>Fe</sub><sup>−1</sup>·s<sup>−1</sup>) as well as the major enhancement of selectivity to light olefins (C<sub>2</sub><sup>=</sup>–C<sub>4</sub><sup>=</sup>). The results for the used catalysts demonstrated that 5 wt% Fe clearly inhibited the sintering of iron particle size and improved the catalytic stability of FTO.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106973"},"PeriodicalIF":5.8,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173024","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}

引用次数: 0

Autogenous water in-situ coke suppression and induced polarization catalytic debromination during calcifying pyrolysis of waste printed circuit boards

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-01-14 DOI: 10.1016/j.jaap.2025.106971

Zhenyu Chen , Huiliang Hou , Lu Zhan , Zhenming Xu , Qinmeng Wang

Removing bromine is crucial for waste printed circuit boards (WPCBs) recycling. Co-pyrolysis calcification is usually regarded as an economical and effective debromination method. However, the coke generated and covered on the surface of calcification agent always reduces the debromination efficiency, hindering the industrial application. In this study, the significant role of autogenous water in both pyrolysis and debromination was revealed during the in-situ monitoring of the co-pyrolysis process of Ca(OH)₂ and WPCBs. Micro morphology characterization showed that autogenous water suppresseed coke formation on the calcification agent surface, which can facilitate the mass transfer for product. Kinetic analysis demonstrated that the pyrolysis apparent activation energy decreased notably from 143–257 kJ/mol to 86.7–147 kJ/mol when water was involved. Through density functional theory (DFT) calculations, we clarified that autogenous water promotes debromination by inducing electron polarization of bromophenol molecules. The pyrolysis oil attained a significant degree of debromination through co-pyrolysis with Ca(OH)₂. 2-bromophenol in the pyrolysis oil was reduced by 86 % and organic brominated components were reduced by 93.6 %. Additionally, light phenols (mono-aromatic phenols) in the pyrolysis oil increased to 96.1 %. This study can inspire innovative debromination agent design paradigms and strategies for bromine removal process.

{"title":"Autogenous water in-situ coke suppression and induced polarization catalytic debromination during calcifying pyrolysis of waste printed circuit boards","authors":"Zhenyu Chen , Huiliang Hou , Lu Zhan , Zhenming Xu , Qinmeng Wang","doi":"10.1016/j.jaap.2025.106971","DOIUrl":"10.1016/j.jaap.2025.106971","url":null,"abstract":"<div><div>Removing bromine is crucial for waste printed circuit boards (WPCBs) recycling. Co-pyrolysis calcification is usually regarded as an economical and effective debromination method. However, the coke generated and covered on the surface of calcification agent always reduces the debromination efficiency, hindering the industrial application. In this study, the significant role of autogenous water in both pyrolysis and debromination was revealed during the in-situ monitoring of the co-pyrolysis process of Ca(OH)<sub>2</sub> and WPCBs. Micro morphology characterization showed that autogenous water suppresseed coke formation on the calcification agent surface, which can facilitate the mass transfer for product. Kinetic analysis demonstrated that the pyrolysis apparent activation energy decreased notably from 143–257 kJ/mol to 86.7–147 kJ/mol when water was involved. Through density functional theory (DFT) calculations, we clarified that autogenous water promotes debromination by inducing electron polarization of bromophenol molecules. The pyrolysis oil attained a significant degree of debromination through co-pyrolysis with Ca(OH)<sub>2</sub>. 2-bromophenol in the pyrolysis oil was reduced by 86 % and organic brominated components were reduced by 93.6 %. Additionally, light phenols (mono-aromatic phenols) in the pyrolysis oil increased to 96.1 %. This study can inspire innovative debromination agent design paradigms and strategies for bromine removal process.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106971"},"PeriodicalIF":5.8,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143174294","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}

引用次数: 0

T-jump pyrolysis of methylphosphonic acid

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-01-14 DOI: 10.1016/j.jaap.2025.106968

Natalie Gese, Hergen Eilers

Methylphosphonic acid (MPA) is an intermediate product of the thermal decomposition of diisopropyl methylphosphonate (DIMP), a compound commonly used as a simulant for chemical warfare agents (CWAs). DIMP’s overall thermal decomposition is rather complex and, despite many investigations, not fully understood, in particular under fast heating conditions. To develop a better understanding of this thermal decomposition process, we investigated the T-jump pyrolysis of MPA and monitor the resulting products using infrared spectroscopy. Throughout the decomposition process, we observed a range of products in heated condensed-phase and vapor-phase MPA, as well as a coating deposited on the optical windows within our sample chamber. The condensation of MPA into larger molecular structures, the generation of methane, ethylene, acetylene, water, CO, CO₂, and possibly an OH-H₂O radical, as well as the emergence of various phosphorus compounds all become evident.

引用次数: 0

On the relation between solubility, chemical structure and pyrolysis of complex hydrocarbon mixtures: Experimental campaign and model

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-01-14 DOI: 10.1016/j.jaap.2025.106959

Elia Colleoni , Vasilios G. Samaras , Chiara Canciani , Paolo Guida , Alessio Frassoldati , Tiziano Faravelli , William L. Roberts

The increasing interest in upgrading residual fuels is driving fundamental research toward a deeper understanding of their properties. Residual fuels, heavy and viscous oils left after crude oil refining, are highly complex mixtures of thousands of different molecules spread over a wide boiling range. Several research efforts have attempted to characterize residual oils over the last century, resulting in the SARA (saturates, aromatics, resins, asphaltenes) analysis being the most widely adopted characterization method. This work showed that a linear combination of the SARA fractions can mimic the actual oil with good accuracy, both in terms of chemical composition and pyrolytic behavior. This is referred to as the additive property in the manuscript. In this work, the additive property was experimentally verified using different experimental techniques (CHNS-O, FT-ICR- MS, and TGA). The validity of such property suggests that neglecting interactions among the different fractions during their pyrolysis is a good approximation, thus enabling the description of the raw fuel on the basis of its main components. This result seems implicitly to confirm that also in the liquid phase large hydrocarbons pyrolyze without strong interactions with the surrounding environments, similarly to what happens in the gas phase. This finding also results in an advantage for model developments, where the pyrolysis of different fuels can be described as a linear combination of SARA-independent models.

{"title":"On the relation between solubility, chemical structure and pyrolysis of complex hydrocarbon mixtures: Experimental campaign and model","authors":"Elia Colleoni , Vasilios G. Samaras , Chiara Canciani , Paolo Guida , Alessio Frassoldati , Tiziano Faravelli , William L. Roberts","doi":"10.1016/j.jaap.2025.106959","DOIUrl":"10.1016/j.jaap.2025.106959","url":null,"abstract":"<div><div>The increasing interest in upgrading residual fuels is driving fundamental research toward a deeper understanding of their properties. Residual fuels, heavy and viscous oils left after crude oil refining, are highly complex mixtures of thousands of different molecules spread over a wide boiling range. Several research efforts have attempted to characterize residual oils over the last century, resulting in the SARA (saturates, aromatics, resins, asphaltenes) analysis being the most widely adopted characterization method. This work showed that a linear combination of the SARA fractions can mimic the actual oil with good accuracy, both in terms of chemical composition and pyrolytic behavior. This is referred to as the additive property in the manuscript. In this work, the additive property was experimentally verified using different experimental techniques (CHNS-O, FT-ICR- MS, and TGA). The validity of such property suggests that neglecting interactions among the different fractions during their pyrolysis is a good approximation, thus enabling the description of the raw fuel on the basis of its main components. This result seems implicitly to confirm that also in the liquid phase large hydrocarbons pyrolyze without strong interactions with the surrounding environments, similarly to what happens in the gas phase. This finding also results in an advantage for model developments, where the pyrolysis of different fuels can be described as a linear combination of SARA-independent models.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106959"},"PeriodicalIF":5.8,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173025","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}

引用次数: 0

Insight into co-pyrolysis behavior of asparagine/fructose mixtures using on-line pyrolysis-GC/MS

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-01-14 DOI: 10.1016/j.jaap.2025.106969

Changrong Luo , Qianqian Yin , Lingjie Zeng , Qian Zhang , Bing Wang , Guijun Yu , Shihao Shen , Wenyan Xie

This study investigated the pyrolysis behavior of asparagine, fructose, and their mixtures under conditions simulating cigarette combustion, using advanced pyrolysis-GC/MS techniques. Results indicated that when asparagine was pyrolyzed alone, it predominantly produced maleimide (97.75 %) and succinimide (2.25 %), likely through intramolecular dehydration, deamination, and subsequent hydrogenation. The co-pyrolysis of asparagine with fructose resulted in a diverse array of products, including numerous nitrogen-containing heterocyclic compounds not present in the individual pyrolysis of either compound and influenced by the ratio of asparagine to fructose. The co-pyrolysis process significantly altered the product distribution and led to a notable reduction in maleimide and succinimide yields. The proportions of main volatile compounds derived from fructose such as 5-HMF, furfural, 2,5-FDA, 5-MF, and DDMP varied from 38.39 %, 35.47 %, 8.13 %, 3.82 % and 1.29 % in individual fructose pyrolysis to 38.93 %, 10.20 %, 0.71 %, 6.87 %, 4.81 % (1:5 ratio) and 44.34 %, 11.97 %, 4.80 %, 4.96 %, and 4.70 % (1:10 ratio), respectively. These findings suggested that three potential pathways were involved in the co-pyrolysis process: the Maillard reaction between asparagine and fructose, the degradation of residual fructose, and independent pyrolysis of partial asparagine. This research provides valuable insights into the complex interactions and product formation mechanisms during co-pyrolysis, contributing to a deeper understanding of smoke chemistry, flavor science, and biofuel production.

{"title":"Insight into co-pyrolysis behavior of asparagine/fructose mixtures using on-line pyrolysis-GC/MS","authors":"Changrong Luo , Qianqian Yin , Lingjie Zeng , Qian Zhang , Bing Wang , Guijun Yu , Shihao Shen , Wenyan Xie","doi":"10.1016/j.jaap.2025.106969","DOIUrl":"10.1016/j.jaap.2025.106969","url":null,"abstract":"<div><div>This study investigated the pyrolysis behavior of asparagine, fructose, and their mixtures under conditions simulating cigarette combustion, using advanced pyrolysis-GC/MS techniques. Results indicated that when asparagine was pyrolyzed alone, it predominantly produced maleimide (97.75 %) and succinimide (2.25 %), likely through intramolecular dehydration, deamination, and subsequent hydrogenation. The co-pyrolysis of asparagine with fructose resulted in a diverse array of products, including numerous nitrogen-containing heterocyclic compounds not present in the individual pyrolysis of either compound and influenced by the ratio of asparagine to fructose. The co-pyrolysis process significantly altered the product distribution and led to a notable reduction in maleimide and succinimide yields. The proportions of main volatile compounds derived from fructose such as 5-HMF, furfural, 2,5-FDA, 5-MF, and DDMP varied from 38.39 %, 35.47 %, 8.13 %, 3.82 % and 1.29 % in individual fructose pyrolysis to 38.93 %, 10.20 %, 0.71 %, 6.87 %, 4.81 % (1:5 ratio) and 44.34 %, 11.97 %, 4.80 %, 4.96 %, and 4.70 % (1:10 ratio), respectively. These findings suggested that three potential pathways were involved in the co-pyrolysis process: the Maillard reaction between asparagine and fructose, the degradation of residual fructose, and independent pyrolysis of partial asparagine. This research provides valuable insights into the complex interactions and product formation mechanisms during co-pyrolysis, contributing to a deeper understanding of smoke chemistry, flavor science, and biofuel production.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106969"},"PeriodicalIF":5.8,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173026","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}

引用次数: 0

Study on the preparation of light aromatics from bituminous coal volatiles catalyzed by Ni-modified USY zeolite

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-01-13 DOI: 10.1016/j.jaap.2025.106967

Jiayu Zhu, Xucheng Zhang, Yingqi Liu, Bochen Xie, Xizhuang Qin, Peng Liang, Tiantian Jiao, Yaqing Zhang

This study examines the influence of metal particle size and dispersion in zeolite-modified catalysts on zeolite structural integrity and catalytic efficiency of coal pyrolysis. Three Ni-modified USY zeolites are synthesized by different methods, and their structure, acidity, and performance of light aromatic hydrocarbons produced by coal catalytic pyrolysis are characterized. The results show that the crystallinity of the ion-exchange Ni-modified USY(E-IX) is greatly reduced, the Ni is uniformly dispersed, the mesoporous specific surface area and the acid content are increased, and the binding energy of Ni²⁺is higher than that of the two impregnation methods. The equivalent-volume water impregnation method (W-I) results in zeolites with suboptimal Ni dispersion, leading to a minor enhancement in acidity and a decrease in specific surface area. Ethanol-impregnated Ni-modified USY (EA-I) shows superior Ni dispersion, a high B acid/L acid ratio, and an increase in mesoporous pore size with a reduced specific surface area. EA-I outperforms other methods, achieving a tar yield of 6.03 % and a light tar percentage of 83.3 %. Compared to USY, the monocyclic aromatic hydrocarbon content increases by 15.5 % and the BTEXN increases to 53.2 %. In different catalysts, the total phenols and oxygen-containing compounds maintain at 40 %, surpassing 35.3 % for raw coal. They facilitate the preferential shift of oxygen to binding to larger molecular radicals. Compared with E-IX and W-I, the yield of EA-I catalyzed BTEXN increased by 31.3 % and 16.2 %, respectively. This research provides valuable insights into the preparation of metal-modified zeolites with small particle sizes and high dispersion for pyrolysis applications.

{"title":"Study on the preparation of light aromatics from bituminous coal volatiles catalyzed by Ni-modified USY zeolite","authors":"Jiayu Zhu, Xucheng Zhang, Yingqi Liu, Bochen Xie, Xizhuang Qin, Peng Liang, Tiantian Jiao, Yaqing Zhang","doi":"10.1016/j.jaap.2025.106967","DOIUrl":"10.1016/j.jaap.2025.106967","url":null,"abstract":"<div><div>This study examines the influence of metal particle size and dispersion in zeolite-modified catalysts on zeolite structural integrity and catalytic efficiency of coal pyrolysis. Three Ni-modified USY zeolites are synthesized by different methods, and their structure, acidity, and performance of light aromatic hydrocarbons produced by coal catalytic pyrolysis are characterized. The results show that the crystallinity of the ion-exchange Ni-modified USY(E-IX) is greatly reduced, the Ni is uniformly dispersed, the mesoporous specific surface area and the acid content are increased, and the binding energy of Ni<sup>2+</sup>is higher than that of the two impregnation methods. The equivalent-volume water impregnation method (W-I) results in zeolites with suboptimal Ni dispersion, leading to a minor enhancement in acidity and a decrease in specific surface area. Ethanol-impregnated Ni-modified USY (EA-I) shows superior Ni dispersion, a high B acid/L acid ratio, and an increase in mesoporous pore size with a reduced specific surface area. EA-I outperforms other methods, achieving a tar yield of 6.03 % and a light tar percentage of 83.3 %. Compared to USY, the monocyclic aromatic hydrocarbon content increases by 15.5 % and the BTEXN increases to 53.2 %. In different catalysts, the total phenols and oxygen-containing compounds maintain at 40 %, surpassing 35.3 % for raw coal. They facilitate the preferential shift of oxygen to binding to larger molecular radicals. Compared with E-IX and W-I, the yield of EA-I catalyzed BTEXN increased by 31.3 % and 16.2 %, respectively. This research provides valuable insights into the preparation of metal-modified zeolites with small particle sizes and high dispersion for pyrolysis applications.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106967"},"PeriodicalIF":5.8,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173018","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}

引用次数: 0

Unraveling the radical pathways: Quinone derivatives formation in the pyrolysis of lignin model compound 2-methoxy-4-propylphenol

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-01-13 DOI: 10.1016/j.jaap.2025.106966

Zhongyue Zhou , Yang Shen , Ru Sun , Xinghua Liu , Hairong Ren , Xintong Xiao , Wang Li , Li Peng , Long Zhao , Fei Qi

Understanding the lignin pyrolysis mechanism holds significant importance for enhancing thermochemical conversion processes and advancing the refinement of biofuels. This investigation explored the pyrolysis of 2-methoxy-4-propylphenol through a comprehensive analysis that combines experimental and theoretical approaches. The experimental results showed the distribution and evolution of free radicals and primary products in the range of 300–750 °C, in which semiquinone radical (SQ) and quinone methide (QM) were dominant. Of particular interest are QMs, which were often overlooked in offline detection but whose existence and importance were demonstrated in our experiments. Theoretical calculation further revealed the initial pyrolysis pathway of 2-methoxy-4-propylphenol. The O-CH₃ bond break and the C-C bond break on the propyl chain were the dominant factors to generate primary free radicals. Further study on the decomposition pathway of main free radicals reconfirmed that QMs were the main decomposition products. Bimolecular reactions, such as radical-assisted abstraction and substitution, were analyzed in detail. These reactions were less important in the present pyrolysis experiments. This study not only provides a comprehensive understanding of the pyrolysis of 2-methoxy-4-propylphenol but also furnishes insights for guiding the conversion of lignin into high-value-added chemicals.

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引用次数: 0

Mechanism of remarkable interference of styrene-butadiene to gasoline identification for fire debris analysis based on TG-IR-GC/MS

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-01-13 DOI: 10.1016/j.jaap.2025.106958

Fanzi Liqiu , Jing Jin , Zhengzhe Zang , Qianqian Zhang , Xiaoxiao Sun , Liang Deng , Jinzhuan Zhang

Matrix interference has been a key but complex topic in forensic science for decades, while its mechanism remains confusing. Based on the preliminary research findings that the combustion/pyrolytic products of styrene-butadiene rubber (SBR) remarkably interfere to gasoline identification in fire debris analysis, this study aims to further trace the source of the remarkable interference and understand the interference mechanism of SBR to gasoline identification. Six types of SBR with different styrene contents were selected, and the corresponding pyrolysis process and pyrolytic products was explored using thermogravimetric analysis-infrared gas chromatography/mass spectrometry (TG-IR-GC/MS). Simultaneously, a comparative analysis was conducted on the pyrolytic products at different pyrolysis stages and the corresponding interference to gasoline identification, and microstructures of SBRs were characterized by Fourier transform infrared spectroscopy (FTIR) to correlate interference with chemical structure further. The results showed that the pyrolysis/combustion process is obviously chemical structure-dependent, and the interference degree of the specific pyrolysis stage can be characterized by the quantity factor of weight loss and the intensity factor from the number of interfering compounds generated during a pyrolysis stage, resulting in the difference in interference degree among different pyrolysis stages. SBR with a lower styrene content produces more interfering pyrolysis products through depolymerization, decomposition, addition, cyclization and aromatization reactions, especially the Diels-Alder reaction involving butadiene with 1,4-units, the products of the reaction serve as precursors to aromatization. From the perspective of chemical structure as well as pyrolysis process, the origin of the matrix interference is systematically discussed in this study, providing important references for understanding, predicting and eliminating matrix interference in fire debris analysis.

{"title":"Mechanism of remarkable interference of styrene-butadiene to gasoline identification for fire debris analysis based on TG-IR-GC/MS","authors":"Fanzi Liqiu , Jing Jin , Zhengzhe Zang , Qianqian Zhang , Xiaoxiao Sun , Liang Deng , Jinzhuan Zhang","doi":"10.1016/j.jaap.2025.106958","DOIUrl":"10.1016/j.jaap.2025.106958","url":null,"abstract":"<div><div>Matrix interference has been a key but complex topic in forensic science for decades, while its mechanism remains confusing. Based on the preliminary research findings that the combustion/pyrolytic products of styrene-butadiene rubber (SBR) remarkably interfere to gasoline identification in fire debris analysis, this study aims to further trace the source of the remarkable interference and understand the interference mechanism of SBR to gasoline identification. Six types of SBR with different styrene contents were selected, and the corresponding pyrolysis process and pyrolytic products was explored using thermogravimetric analysis-infrared gas chromatography/mass spectrometry (TG-IR-GC/MS). Simultaneously, a comparative analysis was conducted on the pyrolytic products at different pyrolysis stages and the corresponding interference to gasoline identification, and microstructures of SBRs were characterized by Fourier transform infrared spectroscopy (FTIR) to correlate interference with chemical structure further. The results showed that the pyrolysis/combustion process is obviously chemical structure-dependent, and the interference degree of the specific pyrolysis stage can be characterized by the quantity factor of weight loss and the intensity factor from the number of interfering compounds generated during a pyrolysis stage, resulting in the difference in interference degree among different pyrolysis stages. SBR with a lower styrene content produces more interfering pyrolysis products through depolymerization, decomposition, addition, cyclization and aromatization reactions, especially the Diels-Alder reaction involving butadiene with 1,4-units, the products of the reaction serve as precursors to aromatization. From the perspective of chemical structure as well as pyrolysis process, the origin of the matrix interference is systematically discussed in this study, providing important references for understanding, predicting and eliminating matrix interference in fire debris analysis.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106958"},"PeriodicalIF":5.8,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173027","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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