Journal of Analytical and Applied Pyrolysis最新文献

Transition-metal-assisted pyrolysis to recover glass fibers from end-of-life wind turbine blades

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-03-06 DOI: 10.1016/j.jaap.2025.107081

Qiang Lu , Haiwen Ji , Yiye Lu , Jie Yang , Weiwei Chen , Jihong Li , Wei Li , Mingxin Xu

The disposal of end-of-life wind turbine blades (WTBs), typically composed of glass fiber-reinforced epoxy resin thermosetting composites, has become a global environmental challenge. Pyrolysis is an effective method for recycling these WTBs, but the process often leads to significant degradation of recovered fibers due to high pyrolysis temperatures. This study proposed a transition-metal-assisted pyrolysis method to enhance the low-temperature depolymerization of end-of-life WTBs, enabling the recovery of glass fibers with improved mechanical properties. With the assistance of ZrCl₄, the resin decomposition ratio of WTBs at 350 °C increased from 52.13 % to 75.59 %, and the tensile strength of the recovered glass fibers improved by 34.74 %. Characterization studies revealed that Zr^4 + ions accelerated the breakdown of C-O-C bonds within the epoxy resin, promoting its decomposition. Additionally, Zr⁴⁺ ions weakened polycondensation and dehydrogenation reactions during the formation of pyrolysis char, reducing its degree of graphitization and improving its oxidative reactivity, thereby shortening the oxidation duration. Consequently, the diffusion of surface defects in the recovered fibers was suppressed, significantly enhancing their mechanical properties. These findings offer valuable insights into addressing the disposal of end-of-life WTBs while simultaneously recovering glass fibers with excellent mechanical properties, thus supporting their circular utilization.

{"title":"Transition-metal-assisted pyrolysis to recover glass fibers from end-of-life wind turbine blades","authors":"Qiang Lu , Haiwen Ji , Yiye Lu , Jie Yang , Weiwei Chen , Jihong Li , Wei Li , Mingxin Xu","doi":"10.1016/j.jaap.2025.107081","DOIUrl":"10.1016/j.jaap.2025.107081","url":null,"abstract":"<div><div>The disposal of end-of-life wind turbine blades (WTBs), typically composed of glass fiber-reinforced epoxy resin thermosetting composites, has become a global environmental challenge. Pyrolysis is an effective method for recycling these WTBs, but the process often leads to significant degradation of recovered fibers due to high pyrolysis temperatures. This study proposed a transition-metal-assisted pyrolysis method to enhance the low-temperature depolymerization of end-of-life WTBs, enabling the recovery of glass fibers with improved mechanical properties. With the assistance of ZrCl<sub>4</sub>, the resin decomposition ratio of WTBs at 350 °C increased from 52.13 % to 75.59 %, and the tensile strength of the recovered glass fibers improved by 34.74 %. Characterization studies revealed that Zr<sup>4 +</sup> ions accelerated the breakdown of C-O-C bonds within the epoxy resin, promoting its decomposition. Additionally, Zr<sup>4+</sup> ions weakened polycondensation and dehydrogenation reactions during the formation of pyrolysis char, reducing its degree of graphitization and improving its oxidative reactivity, thereby shortening the oxidation duration. Consequently, the diffusion of surface defects in the recovered fibers was suppressed, significantly enhancing their mechanical properties. These findings offer valuable insights into addressing the disposal of end-of-life WTBs while simultaneously recovering glass fibers with excellent mechanical properties, thus supporting their circular utilization.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107081"},"PeriodicalIF":5.8,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563393","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

Sulfur dioxide extrusion: Exploring the mechanism behind the formation of highly reactive 5-(trifluoromethyl)azafulvenium methide intermediates

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-03-04 DOI: 10.1016/j.jaap.2025.107085

Diana C. Pinilla Peña , Guadalupe Firpo , Noelia M. Ceballos , Federico J. Velazco , Gloria Patricia Camargo Solorzano , María I. L. Soares , Liliana B. Pierella , Teresa M.V.D. Pinho e Melo , Walter J. Peláez

Pyrolysis reactions of 2,2-dioxo-7-(trifluoromethyl)-1H,3H-pyrrolo[1,2-c]thiazoles are presented. Thermal reactions lead to the formation of noteworthy 5-membered heterocyclic products, whose yields were higher when FVPN2 was performed compared to other synthetic pyrolysis methods, such as microwave-induced pyrolysis (MWIP) or conventional heating (reflux). Trifluoromethyl-substituted pyrroles were obtained via rearrangements of trifluoromethyl-azafulvenium-methide intermediates. The experimental Arrhenius parameters of FVPN2 are presented for the very first time, and the results enable the proposal of three distinct mechanistic pathways for the SO₂ extrusion process occurring at high temperatures. Quantum chemical calculations performed at the DFT level of theory provided a rational explanation for the observed results.

{"title":"Sulfur dioxide extrusion: Exploring the mechanism behind the formation of highly reactive 5-(trifluoromethyl)azafulvenium methide intermediates","authors":"Diana C. Pinilla Peña , Guadalupe Firpo , Noelia M. Ceballos , Federico J. Velazco , Gloria Patricia Camargo Solorzano , María I. L. Soares , Liliana B. Pierella , Teresa M.V.D. Pinho e Melo , Walter J. Peláez","doi":"10.1016/j.jaap.2025.107085","DOIUrl":"10.1016/j.jaap.2025.107085","url":null,"abstract":"<div><div>Pyrolysis reactions of 2,2-dioxo-7-(trifluoromethyl)-1<em>H</em>,3<em>H</em>-pyrrolo[1,2-<em>c</em>]thiazoles are presented. Thermal reactions lead to the formation of noteworthy 5-membered heterocyclic products, whose yields were higher when FVPN2 was performed compared to other synthetic pyrolysis methods, such as microwave-induced pyrolysis (MWIP) or conventional heating (reflux). Trifluoromethyl-substituted pyrroles were obtained via rearrangements of trifluoromethyl-azafulvenium-methide intermediates. The experimental Arrhenius parameters of FVPN2 are presented for the very first time, and the results enable the proposal of three distinct mechanistic pathways for the SO<sub>2</sub> extrusion process occurring at high temperatures. Quantum chemical calculations performed at the DFT level of theory provided a rational explanation for the observed results.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107085"},"PeriodicalIF":5.8,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563394","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

Differences in pyrolysis behaviors of tar-rich coal macerals from various paleosedimentary environments

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-03-04 DOI: 10.1016/j.jaap.2025.107067

Yaya Shi , Qingmin Shi , Shuangming Wang , Chunhao Li , Shidong Cui , Fu Yang , Bingyang Kou

Tar-rich coal, a valuable resource for China's energy security, undergoes the production of tar and gas during pyrolysis. This study combines proximate and ultimate analyses with TGA and in-situ FTIR to investigate the molecular structure of raw coal and its macerals from three coal-forming environments. The results indicate that the paleosedimentary environment significantly affects coal structure, especially the aliphatic and aromatic structures, as well as oxygenated functional groups. Deeper overlying water and more reducing conditions foster the formation of aliphatic structures, which are abundant in vitrinite-rich concentrates and raw coal, whereas inertinite-rich concentrates contain fewer. During pyrolysis, aromatic C-H condensation results in the formation of semi-coke and coke. Raw coal and macerals from deeper, reducing environments decompose more rapidly, accelerating aromatic condensation. Additionally, volatile gases such as H₂, CO, CO₂, CH₄, and tar are generated during pyrolysis. CO and CO₂ mainly originate from the cracking of oxygenated functional groups. Xinjiang raw coal(T1-R(V)), formed under deep overlying water, exhibits intense decomposition due to the high content of oxygenated functional groups in aliphatic side chains. Xiwan coal(T3), from a wet forest swamp environment, has numerous oxygenated groups, leading to higher decomposition rates in raw coal and inertinite-rich concentrates. Aliphatic cracking releases hydrocarbon gases and tar, with faster decomposition occurring in deeper, reducing environments. The thermal decomposition rates of vitrinite-rich concentrates show minimal variation. These findings underscore the influence of coal-forming environments on pyrolysis, facilitating the efficient utilization of tar-rich coal.

{"title":"Differences in pyrolysis behaviors of tar-rich coal macerals from various paleosedimentary environments","authors":"Yaya Shi , Qingmin Shi , Shuangming Wang , Chunhao Li , Shidong Cui , Fu Yang , Bingyang Kou","doi":"10.1016/j.jaap.2025.107067","DOIUrl":"10.1016/j.jaap.2025.107067","url":null,"abstract":"<div><div>Tar-rich coal, a valuable resource for China's energy security, undergoes the production of tar and gas during pyrolysis. This study combines proximate and ultimate analyses with TGA and in-situ FTIR to investigate the molecular structure of raw coal and its macerals from three coal-forming environments. The results indicate that the paleosedimentary environment significantly affects coal structure, especially the aliphatic and aromatic structures, as well as oxygenated functional groups. Deeper overlying water and more reducing conditions foster the formation of aliphatic structures, which are abundant in vitrinite-rich concentrates and raw coal, whereas inertinite-rich concentrates contain fewer. During pyrolysis, aromatic C-H condensation results in the formation of semi-coke and coke. Raw coal and macerals from deeper, reducing environments decompose more rapidly, accelerating aromatic condensation. Additionally, volatile gases such as H₂, CO, CO₂, CH₄, and tar are generated during pyrolysis. CO and CO₂ mainly originate from the cracking of oxygenated functional groups. Xinjiang raw coal(T1-R(V)), formed under deep overlying water, exhibits intense decomposition due to the high content of oxygenated functional groups in aliphatic side chains. Xiwan coal(T3), from a wet forest swamp environment, has numerous oxygenated groups, leading to higher decomposition rates in raw coal and inertinite-rich concentrates. Aliphatic cracking releases hydrocarbon gases and tar, with faster decomposition occurring in deeper, reducing environments. The thermal decomposition rates of vitrinite-rich concentrates show minimal variation. These findings underscore the influence of coal-forming environments on pyrolysis, facilitating the efficient utilization of tar-rich coal.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107067"},"PeriodicalIF":5.8,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549743","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 the characteristics of microwave-assisted co-pyrolysis of biomass and waste plastics based on orthogonal experimental methods: Thermal degradation, kinetics and product distribution

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-03-03 DOI: 10.1016/j.jaap.2025.107083

Wen Teng , Zhaosheng Yu , Gao Shen , Huirong Ni , Xiaoqian Ma

This research explores the synergistic effects and distribution of liquid products during microwave-assisted co-pyrolysis (MACP) of eucalyptus wood (EW) and polypropylene (PP). Firstly, thermal degradation and kinetics, of co-pyrolysis of EW and PP were investigated. The minimum average activation energy was observed at a mixing ratio of 50 % EW to 50 % PP, measuring 187.98 kJ/mol (KAS) and 189.82 kJ/mol (OFW), respectively. The effects of pyrolysis temperature, material ratio and microwave absorbent amount on the MACP of EW and PP were investigated based on the Orthogonal Design of Experiments (OED) method. The yield of three-phase product and chemical composition of liquid product were analyzed. The results indicated that the MACP of EW and PP significantly enhanced both the yield and quality of bio-oil. Optimal oil yield was achieved through MACP of EW and PP at 550℃ with a ratio of 30 % EW, 70 % PP, and 120 wt% microwave absorbent (SiC). The content of aromatic hydrocarbons peaked at the material ratio of 50 % EW and 50 % PP (E5P5) (42.53 %), while the content of monocyclic aromatic hydrocarbons (MAHs) was 3.59 %. The peak content of MAHs occurred at 550 ℃, but further temperature increase resulted in the transformation of MAHs into polycyclic aromatic hydrocarbons (PAHs). To optimize the content of MAHs in pyrolysis oil, the optimal MACP conditions are 550 ℃, E5P5 and 120 wt%SiC. The results of this research can act as a significant reference and offer practical insights for the effective generation of hydrocarbon-rich bio-oil via the MACP process involving biomass and waste plastics.

{"title":"Investigation of the characteristics of microwave-assisted co-pyrolysis of biomass and waste plastics based on orthogonal experimental methods: Thermal degradation, kinetics and product distribution","authors":"Wen Teng , Zhaosheng Yu , Gao Shen , Huirong Ni , Xiaoqian Ma","doi":"10.1016/j.jaap.2025.107083","DOIUrl":"10.1016/j.jaap.2025.107083","url":null,"abstract":"<div><div>This research explores the synergistic effects and distribution of liquid products during microwave-assisted co-pyrolysis (MACP) of eucalyptus wood (EW) and polypropylene (PP). Firstly, thermal degradation and kinetics, of co-pyrolysis of EW and PP were investigated. The minimum average activation energy was observed at a mixing ratio of 50 % EW to 50 % PP, measuring 187.98 kJ/mol (KAS) and 189.82 kJ/mol (OFW), respectively. The effects of pyrolysis temperature, material ratio and microwave absorbent amount on the MACP of EW and PP were investigated based on the Orthogonal Design of Experiments (OED) method. The yield of three-phase product and chemical composition of liquid product were analyzed. The results indicated that the MACP of EW and PP significantly enhanced both the yield and quality of bio-oil. Optimal oil yield was achieved through MACP of EW and PP at 550℃ with a ratio of 30 % EW, 70 % PP, and 120 wt% microwave absorbent (SiC). The content of aromatic hydrocarbons peaked at the material ratio of 50 % EW and 50 % PP (E5P5) (42.53 %), while the content of monocyclic aromatic hydrocarbons (MAHs) was 3.59 %. The peak content of MAHs occurred at 550 ℃, but further temperature increase resulted in the transformation of MAHs into polycyclic aromatic hydrocarbons (PAHs). To optimize the content of MAHs in pyrolysis oil, the optimal MACP conditions are 550 ℃, E5P5 and 120 wt%SiC. The results of this research can act as a significant reference and offer practical insights for the effective generation of hydrocarbon-rich bio-oil via the MACP process involving biomass and waste plastics.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107083"},"PeriodicalIF":5.8,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549747","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

Comprehensive valorization of oil-rich food waste through coupling transesterification with pyrolysis

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-03-03 DOI: 10.1016/j.jaap.2025.107082

Gyeongnam Park , Taewoo Lee , Jung-Hun Kim , Hocheol Song , Wei-Hsin Chen , Eilhann E. Kwon

Recent shifts in food consumption trends toward fried foods have increased the generation of oil-rich food waste. Although biological processes show promise for the food waste valorization, the presence of oil components limits microbial activity. This study proposes a thermochemical approach for valorizing oil-rich fried debris, a by-product of deep-frying, by coupling transesterification with pyrolysis. Characterization of fried-debris-extracted oil (FDO) revealed high impurity levels, free fatty acids and aldehydes. This necessitates transesterification method with more tolerance to these impurities than the conventional acid-treated process. A thermally-induced transesterification demonstrated the impurity tolerance, representing biodiesel yield exceeding 95 wt% regardless of the mixing ratio of aldehyde-to-refined olive oil. When applying to FDO, this process yielded a consistent biodiesel output (41.1 wt%), representing a 1.43-fold increase compared with the conventional transesterification. As a strategy for the comprehensive valorization of fried debris, de-fatted fried debris (DFD) remaining after oil extraction was further pyrolyzed. To impart a sustainability to the pyrolysis system, CO₂ was employed as a reactive agent. CO₂ showed a reactivity of converting DFD-derived volatiles into syngas, particularly CO, while producing biochar. The CO₂ reactivity was accelerated when conducting catalytic pyrolysis over Ni catalyst, resulting in 71.43 wt% syngas and 18.47 wt% biochar. To evaluate the environmental benefits of this process, the CO₂ mitigation potential of biodiesel, syngas, and biochar was estimated, representing an annual reduction of 14.24 × 10⁸ kg CO₂ in South Korea.

{"title":"Comprehensive valorization of oil-rich food waste through coupling transesterification with pyrolysis","authors":"Gyeongnam Park , Taewoo Lee , Jung-Hun Kim , Hocheol Song , Wei-Hsin Chen , Eilhann E. Kwon","doi":"10.1016/j.jaap.2025.107082","DOIUrl":"10.1016/j.jaap.2025.107082","url":null,"abstract":"<div><div>Recent shifts in food consumption trends toward fried foods have increased the generation of oil-rich food waste. Although biological processes show promise for the food waste valorization, the presence of oil components limits microbial activity. This study proposes a thermochemical approach for valorizing oil-rich fried debris, a by-product of deep-frying, by coupling transesterification with pyrolysis. Characterization of fried-debris-extracted oil (FDO) revealed high impurity levels, free fatty acids and aldehydes. This necessitates transesterification method with more tolerance to these impurities than the conventional acid-treated process. A thermally-induced transesterification demonstrated the impurity tolerance, representing biodiesel yield exceeding 95 wt% regardless of the mixing ratio of aldehyde-to-refined olive oil. When applying to FDO, this process yielded a consistent biodiesel output (41.1 wt%), representing a 1.43-fold increase compared with the conventional transesterification. As a strategy for the comprehensive valorization of fried debris, de-fatted fried debris (DFD) remaining after oil extraction was further pyrolyzed. To impart a sustainability to the pyrolysis system, CO<sub>2</sub> was employed as a reactive agent. CO<sub>2</sub> showed a reactivity of converting DFD-derived volatiles into syngas, particularly CO, while producing biochar. The CO<sub>2</sub> reactivity was accelerated when conducting catalytic pyrolysis over Ni catalyst, resulting in 71.43 wt% syngas and 18.47 wt% biochar. To evaluate the environmental benefits of this process, the CO<sub>2</sub> mitigation potential of biodiesel, syngas, and biochar was estimated, representing an annual reduction of 14.24 × 10<sup>8</sup> kg CO<sub>2</sub> in South Korea.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107082"},"PeriodicalIF":5.8,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549745","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

Efficient catalytic hydroconversion of phenolic-rich aromatic compounds from the extraction of coal tar residue to cyclanes over a β/M composite zeolite-supported Ni nanoparticles

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-03-03 DOI: 10.1016/j.jaap.2025.107069

Wen-Ao Shi , Zhong-Hao Jiang , Ni Bai , Ai-Min Wang , Ai-Rong Mao , Zi-Long Zhao , Lin Lang , Jian Wei , Hai-Yan Liu , Qing-Qing Sun , Yong Gao , Yu-Hong Kang , Yan-Jun Li , Jin-Jun Bai

The separation of condensed aromatic compounds from coal tar residue (CTR), converted into cyclanes via catalytic hydroconversion (CHC) to produce essential blending components for coal-based jet fuel, represents a significant strategy for enhancing CTR's value. A highly efficient bifunctional catalyst was prepared by loading Ni nanoparticles (NNPs, ca. 10 %) on β/MCM-41 composite zeolite (β/M) and denoted as Ni₁₀_%@β/M. CTR was sequentially extracted with acetone/carbon disulfide, petroleum ether, and petroleum ether/methanol (5 vol% H₂O) to obtain the soluble portion in methanol phase (PEEP_M). PEEP_M mainly consists of phenols (64.8 %) and arenes (18.9 %). It was conducted to CHC over Ni₁₀_%@β/M at 160 °C for 16 h under 5 MPa of an initial hydrogen pressure (IHP) to obtain CHPEEP_M. The results indicate that the relative content of cyclanes in CHPEEP_M reaches as high as 93.4 %. In Ni₁₀_%@β/M, abundant defects, hierarchical porous composite zeolite with strong Lewis acid sites and uniformly dispersed NNPs play crucial roles in removing heteroatoms and hydrogenating aromatic rings (ARs), respectively. Benzyloxybenzene (BOB) is a model compound with a >C-O- bridge bond and ARs, used to study the catalytic activity of Ni₁₀_%@β/M. BOB was completely converted into cyclanes at 160 °C for 2 h under 5 MPa IHP. The high yield of polycyclic alkanes is related to the coupling between the active fragments formed after >C-O- cleavage and the main structure. The synergistic transfer of H···H, ^δ+H···H^δ-, and H⁺ generated by Ni₁₀_%@β/M activation of H₂ is key to the hydrogenation of ARs via induced >C-O- bond cleavage, leading to the formation of saturated cyclanes.

{"title":"Efficient catalytic hydroconversion of phenolic-rich aromatic compounds from the extraction of coal tar residue to cyclanes over a β/M composite zeolite-supported Ni nanoparticles","authors":"Wen-Ao Shi , Zhong-Hao Jiang , Ni Bai , Ai-Min Wang , Ai-Rong Mao , Zi-Long Zhao , Lin Lang , Jian Wei , Hai-Yan Liu , Qing-Qing Sun , Yong Gao , Yu-Hong Kang , Yan-Jun Li , Jin-Jun Bai","doi":"10.1016/j.jaap.2025.107069","DOIUrl":"10.1016/j.jaap.2025.107069","url":null,"abstract":"<div><div>The separation of condensed aromatic compounds from coal tar residue (CTR), converted into cyclanes via catalytic hydroconversion (CHC) to produce essential blending components for coal-based jet fuel, represents a significant strategy for enhancing CTR's value. A highly efficient bifunctional catalyst was prepared by loading Ni nanoparticles (NNPs, <em>ca</em>. 10 %) on <em>β</em>/MCM-41 composite zeolite (<em>β</em>/<em>M)</em> and denoted as Ni<sub>10</sub><sub>%</sub>@<em>β</em>/<em>M</em>. CTR was sequentially extracted with acetone/carbon disulfide, petroleum ether, and petroleum ether/methanol (5 vol% H<sub>2</sub>O) to obtain the soluble portion in methanol phase (PEEP<sub>M</sub>). PEEP<sub>M</sub> mainly consists of phenols (64.8 %) and arenes (18.9 %). It was conducted to CHC over Ni<sub>10</sub><sub>%</sub>@<em>β</em>/<em>M</em> at 160 °C for 16 h under 5 MPa of an initial hydrogen pressure (IHP) to obtain CHPEEP<sub>M</sub>. The results indicate that the relative content of cyclanes in CHPEEP<sub>M</sub> reaches as high as 93.4 %. In Ni<sub>10</sub><sub>%</sub>@<em>β</em>/<em>M</em>, abundant defects, hierarchical porous composite zeolite with strong Lewis acid sites and uniformly dispersed NNPs play crucial roles in removing heteroatoms and hydrogenating aromatic rings (ARs), respectively. Benzyloxybenzene (BOB) is a model compound with a >C-O- bridge bond and ARs, used to study the catalytic activity of Ni<sub>10</sub><sub>%</sub>@<em>β</em>/<em>M</em>. BOB was completely converted into cyclanes at 160 °C for 2 h under 5 MPa IHP. The high yield of polycyclic alkanes is related to the coupling between the active fragments formed after >C-O- cleavage and the main structure. The synergistic transfer of H···H, <sup>δ+</sup>H···H<sup>δ-</sup>, and H<sup>+</sup> generated by Ni<sub>10</sub><sub>%</sub>@<em>β</em>/<em>M</em> activation of H<sub>2</sub> is key to the hydrogenation of ARs via induced >C-O- bond cleavage, leading to the formation of saturated cyclanes.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107069"},"PeriodicalIF":5.8,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549744","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 thermal decomposition behavior of methyl ethyl ketone peroxide in acid, alkali and water environments

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-03-03 DOI: 10.1016/j.jaap.2025.107078

Zhen Xu, Wei Gao

Methyl ethyl ketone peroxide (MEKPO) is a highly reactive chemical substance that exhibits different thermal decomposition behaviors under different environmental conditions such as acid, alkali, and water. This article uses a microcalorimeter (C80) and a thermogravimetric infrared mass spectrometry (TGA-IR-GC/MS) system to study the thermal decomposition characteristics of MEKPO doped with different mass fractions of water (H₂O), dilute sulfuric acid (H₂SO₄), and sodium hydroxide solution (NaOH), including changes in kinetic parameters and reaction pathways. The results indicate that MEKPO pyrolysis is divided into two steps, with the first stage being the main one. The reaction rate is highest at the beginning of the reaction and then decreases continuously with the increase of conversion degree. The increase in acid and water content promotes the two-step decomposition of MEKPO, reducing the initial decomposition temperature of its main exothermic peak (Peak I) by 11.8℃ and 9.3℃, respectively The total heat release increased by 40.5 % and 37.9 %. Adding alkali will make the thermal decomposition of MEKPO more concentrated in the early stage of the reaction (50–150℃), and induce two unseparated exothermic peaks during this stage. The pyrolysis products of MEKPO mainly include CH₂O₂, CH₃O, C₂H₄O₂, C₄H₈O, C₃H₆O₂, C₅H₁₂O, C₄H₁₀O₃, etc. Adding acid, alkali, and water can affect the peak time of some products, and even cause some products to completely disappear, thereby affecting the mechanism of the entire decomposition reaction.

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引用次数: 0

Multi-objective optimization framework for nitrogen-containing compounds generation in nitrogen-enriched pyrolysis: Integrating transfer learning and experimental validation

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-03-01 DOI: 10.1016/j.jaap.2025.107070

Hui Wang , Dongmei Bi , Qingqing Qian , Lei Pan , Shanjian Liu , Weiming Yi

A multi-objective optimization approach, integrating machine learning and transfer learning, was proposed to optimize the generation of nitrogen-containing compounds in nitrogen-enriched pyrolysis of biomass. A high-accuracy Gradient Boosting Regression Tree (GBRT) model was developed using 827 experimental data sets, with transfer learning employed to accelerate training on specific target variables. This approach significantly enhanced both learning efficiency and predictive performance. The model achieved a Coefficient of Determination (R²) of 0.968 and a Mean Absolute Error (MAE) of 1.047 on the test set, demonstrating exceptional predictive capability. Through Principal Component Analysis (PCA) and model interpretability methods such as SHapley Additive exPlanations (SHAP) and Local Interpretable Model-agnostic Explanations (LIME), key influencing factors were identified. The critical factors include nitrogen source ratio, pyrolysis temperature, and protective gas. The study identified a synergistic effect when the nitrogen source ratio was 50.00 % and the pyrolysis temperature was 550°C. This condition led to the maximum generation of nitrogen-containing compounds. Additionally, increasing the nitrogen source ratio reduced the formation of volatile compounds, while higher lignin content promoted the formation of aldehydes and ketones. Experimental validation via nitrogen-enriched pyrolysis of corn stover confirmed the practical applicability of the model. The model accurately predicted nitrogen-containing compounds generation, with the maximum prediction error constrained to within 6.20 %. This study combines data-driven methods with experimental validation. The approach provides a novel technological framework for optimizing complex chemical reactions and supporting the sustainable production of high-value nitrogen-based chemicals.

{"title":"Multi-objective optimization framework for nitrogen-containing compounds generation in nitrogen-enriched pyrolysis: Integrating transfer learning and experimental validation","authors":"Hui Wang , Dongmei Bi , Qingqing Qian , Lei Pan , Shanjian Liu , Weiming Yi","doi":"10.1016/j.jaap.2025.107070","DOIUrl":"10.1016/j.jaap.2025.107070","url":null,"abstract":"<div><div>A multi-objective optimization approach, integrating machine learning and transfer learning, was proposed to optimize the generation of nitrogen-containing compounds in nitrogen-enriched pyrolysis of biomass. A high-accuracy Gradient Boosting Regression Tree (GBRT) model was developed using 827 experimental data sets, with transfer learning employed to accelerate training on specific target variables. This approach significantly enhanced both learning efficiency and predictive performance. The model achieved a Coefficient of Determination (R²) of 0.968 and a Mean Absolute Error (MAE) of 1.047 on the test set, demonstrating exceptional predictive capability. Through Principal Component Analysis (PCA) and model interpretability methods such as SHapley Additive exPlanations (SHAP) and Local Interpretable Model-agnostic Explanations (LIME), key influencing factors were identified. The critical factors include nitrogen source ratio, pyrolysis temperature, and protective gas. The study identified a synergistic effect when the nitrogen source ratio was 50.00 % and the pyrolysis temperature was 550°C. This condition led to the maximum generation of nitrogen-containing compounds. Additionally, increasing the nitrogen source ratio reduced the formation of volatile compounds, while higher lignin content promoted the formation of aldehydes and ketones. Experimental validation via nitrogen-enriched pyrolysis of corn stover confirmed the practical applicability of the model. The model accurately predicted nitrogen-containing compounds generation, with the maximum prediction error constrained to within 6.20 %. This study combines data-driven methods with experimental validation. The approach provides a novel technological framework for optimizing complex chemical reactions and supporting the sustainable production of high-value nitrogen-based chemicals.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107070"},"PeriodicalIF":5.8,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143534431","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

Catalytic conversion of polymer waste into high-value products for advancing circular economy and eco-sustainability

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-02-28 DOI: 10.1016/j.jaap.2025.107052

Rani Bushra , Areeba Khayal , Mehraj Ahmad , Junlong Song , Yongcan Jin , Huining Xiao

Global demands for more effective plastic waste management have driven significant advancements in recycling technologies, yet many of these approaches continue to face considerable economic and technical limitations. As a game-changing concept, upcycling builds on the inherent value of plastic waste by transforming it into specialized, high-value commodities with clear environmental and economic benefits. A key priority lies in addressing the degradation of non-recoverable plastic waste to mitigate persistent pollution concerns. This review provides a comprehensive assessment of emerging plastic conversion technologies, accentuating the transition from conventional recycling to innovative upcycling methods designed to produce premium fuels, chemicals, and materials. In particular, recent breakthroughs in catalytic degradation are examined, detailing the transformation of plastics into biodegradable or environmentally non-toxic products and, in some cases, the complete combustion of polymers into carbon dioxide and water. Emphasizing advanced technologies that go beyond established recycling paradigms, the review underscores upcycling’s potential to address the escalating plastic waste crisis. Further, this discussion investigates how circular economy principles–specifically the reduction, reuse and redesign of plastic productscan reshape the plastic lifecycle and yield superior environmental outcomes. Collaborative initiatives among industry, academia, and policymakers, aimed at driving the field of plastic conversion in new directions, are evaluated. Multiple case studies and pilot projects demonstrate the feasibility and scalability of these cutting-edge approaches in real-world contexts. Finally, the review identifies critical barriers to widespread implementation of advanced plastic conversion technologies and proposes strategic measures to refine upcycling methods. Taken together, these insights call for the global integration of next-generation plastic conversion practices, thereby strengthening environmental sustainability and driving the transition toward a more circular plastic economy.

{"title":"Catalytic conversion of polymer waste into high-value products for advancing circular economy and eco-sustainability","authors":"Rani Bushra , Areeba Khayal , Mehraj Ahmad , Junlong Song , Yongcan Jin , Huining Xiao","doi":"10.1016/j.jaap.2025.107052","DOIUrl":"10.1016/j.jaap.2025.107052","url":null,"abstract":"<div><div>Global demands for more effective plastic waste management have driven significant advancements in recycling technologies, yet many of these approaches continue to face considerable economic and technical limitations. As a game-changing concept, upcycling builds on the inherent value of plastic waste by transforming it into specialized, high-value commodities with clear environmental and economic benefits. A key priority lies in addressing the degradation of non-recoverable plastic waste to mitigate persistent pollution concerns. This review provides a comprehensive assessment of emerging plastic conversion technologies, accentuating the transition from conventional recycling to innovative upcycling methods designed to produce premium fuels, chemicals, and materials. In particular, recent breakthroughs in catalytic degradation are examined, detailing the transformation of plastics into biodegradable or environmentally non-toxic products and, in some cases, the complete combustion of polymers into carbon dioxide and water. Emphasizing advanced technologies that go beyond established recycling paradigms, the review underscores upcycling’s potential to address the escalating plastic waste crisis. Further, this discussion investigates how circular economy principles–specifically the reduction, reuse and redesign of plastic products<img>can reshape the plastic lifecycle and yield superior environmental outcomes. Collaborative initiatives among industry, academia, and policymakers, aimed at driving the field of plastic conversion in new directions, are evaluated. Multiple case studies and pilot projects demonstrate the feasibility and scalability of these cutting-edge approaches in real-world contexts. Finally, the review identifies critical barriers to widespread implementation of advanced plastic conversion technologies and proposes strategic measures to refine upcycling methods. Taken together, these insights call for the global integration of next-generation plastic conversion practices, thereby strengthening environmental sustainability and driving the transition toward a more circular plastic economy.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"189 ","pages":"Article 107052"},"PeriodicalIF":5.8,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143549746","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

Gas-phase catalysis of coal fast pyrolysis volatiles over acid, base and acid-base composite catalysts and the catalysts coking behavior 煤快速热解挥发物在酸、碱和酸碱复合催化剂上的气相催化以及催化剂的结焦行为

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2025-02-28 DOI: 10.1016/j.jaap.2025.107068

Jing-Xian Wang , Xuan-Jie Zou , Yu-Gui Yang , Wen-Long Xu , Yan-Chao Shang , Cheng-Biao Wang , Pei-Jie Zong , Yi-Nan Yang , Da-Meng Wang , Ning Wang , Ying-Yun Qiao , Yuan-Yu Tian

The gas-phase catalytic upgrading of coal rapid pyrolysis volatiles is a promising strategy for achieving high-value utilization. The catalytic reforming characteristics of coal rapid pyrolysis volatiles over solid base catalyst (calcium aluminate, AlCa), acid catalyst (HZSM-5, Z5), and acid-base composite catalyst (AlCa-Z5) were investigated using a falling bed reactor. The composition and properties of coke deposits on various catalysts were systematically compared and evaluated using NH₄/CO₂-TPD, XPS, Raman spectroscopy, and temperature programmed oxidation (TPO). The findings indicate that AlCa and Z5 markedly increased olefins and aromatics in tar, respectively, and the AlCa-Z5 elevated olefins, aromatics and phenols to over 70 %. The coke mainly deposited on strongly basic and acidic sites, predominantly blocking the 2–6, 1–2, and 0–6 nm pore channels of the AlCa, Z5, and AlCa-Z5 catalysts, respectively. AlCa formed less catalytic coke than the Z5 (48.76 vs. 60.09 %), although the coke graphitization and particle size were greater owing to its exceptional dehydrogenation properties. Specifically, the graphitization and particle size of coke formed on AlCa-Z5 were remarkably reduced. The oxidative weight loss temperature of thermal coke is around 450 °C, while the catalytic coke on AlCa reaches up to 720 °C, over 100 °C higher than that of Z5. The CC/C-C structures (>80 %) dominate in coke, exhibiting more O-CO on AlCa and more C-O on Z5. The research results support the advancement and industrialization of coal hierarchical pyrolysis gas-phase catalytic cracking technology.

煤炭快速热解挥发物的气相催化升级是实现高值化利用的一种可行策略。研究人员使用下降床反应器研究了煤快速热解挥发物在固体碱催化剂（铝酸钙，AlCa）、酸性催化剂（HZSM-5，Z5）和酸碱复合催化剂（AlCa-Z5）上的催化重整特性。使用 NH4/CO2-TPD、XPS、拉曼光谱和温度编程氧化 (TPO) 系统地比较和评估了各种催化剂上焦炭沉积物的组成和性质。研究结果表明，AlCa 和 Z5 分别显著增加了焦油中的烯烃和芳烃含量，而 AlCa-Z5 则将烯烃、芳烃和酚的含量提高到 70% 以上。焦炭主要沉积在强碱性和酸性位点上，分别主要堵塞了 AlCa、Z5 和 AlCa-Z5 催化剂的 2-6、1-2 和 0-6 nm 孔道。与 Z5 相比，AlCa 形成的催化焦炭更少（48.76% 对 60.09%），但由于其特殊的脱氢特性，焦炭的石墨化程度和颗粒尺寸更大。具体而言，AlCa-Z5 上形成的焦炭石墨化程度和粒度都明显降低。热焦炭的氧化失重温度约为 450 °C，而 AlCa 上的催化焦炭温度高达 720 °C，比 Z5 高出 100 °C。焦炭中主要是 CC/C-C 结构（80%），在 AlCa 上表现出更多的 O-CO，而在 Z5 上则表现出更多的 C-O。该研究成果为煤分层热解气相催化裂化技术的发展和工业化提供了支持。

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引用次数: 0