Pub Date : 2024-11-28DOI: 10.1016/j.jaap.2024.106883
Yanbo Yang , Mo Chu , Min Gao , Jianxin Li , Lingqi Zhu , Hui Wang
The thermal fragmentation of low-rank coal had been proven to be a new way of desulfurization for char with coarse-size. However, whether harmful trace elements (HTEs) could be effectively removed in coarse-size char by thermal fragmentation action demand for further study. Two high-sulfur low-rank coals were used to explore the distribution behavior of As, Cr, Cu, Mn, and Pb in thermal fragmentation char with different particle sizes obtained by the fixed-bed and rotary kiln pyrolysis. Combined with the occurrence forms of HTEs in raw coal and volatilization characteristics of HTEs obtained by thermodynamic simulation software, the distribution of HTEs in thermal fragmentation char was analyzed. The effectiveness of thermal fragmentation of HTEs components in fixed-bed pyrolysis was reliant on high temperatures, with poor distribution resulting in less than 20 % of As, Cu, and Pb components being allocated to pulverization char. The thermal fragmentation of Cu components in disulfide form, was severely hindered by the binding effect of metaplast. In contrast, rotary kiln pyrolysis facilitated a greater distribution proportion of HTEs components into pulverization char at lower temperatures. Under optimal conditions, the distribution of As, Pb, and Cr into pulverization char surpassed 70 %. The strengthening thermal fragmentation in the rotary kiln reduce the binding effects, effectively increasing the distribution of copper-rich components into pulverized char.
{"title":"Distribution characteristics of trace elements (As/Cr/Mn/Cu/Pb) in the thermal fragmentation and strengthening fragmentation processes of low-rank coal with high sulfur content","authors":"Yanbo Yang , Mo Chu , Min Gao , Jianxin Li , Lingqi Zhu , Hui Wang","doi":"10.1016/j.jaap.2024.106883","DOIUrl":"10.1016/j.jaap.2024.106883","url":null,"abstract":"<div><div>The thermal fragmentation of low-rank coal had been proven to be a new way of desulfurization for char with coarse-size. However, whether harmful trace elements (HTEs) could be effectively removed in coarse-size char by thermal fragmentation action demand for further study. Two high-sulfur low-rank coals were used to explore the distribution behavior of As, Cr, Cu, Mn, and Pb in thermal fragmentation char with different particle sizes obtained by the fixed-bed and rotary kiln pyrolysis. Combined with the occurrence forms of HTEs in raw coal and volatilization characteristics of HTEs obtained by thermodynamic simulation software, the distribution of HTEs in thermal fragmentation char was analyzed. The effectiveness of thermal fragmentation of HTEs components in fixed-bed pyrolysis was reliant on high temperatures, with poor distribution resulting in less than 20 % of As, Cu, and Pb components being allocated to pulverization char. The thermal fragmentation of Cu components in disulfide form, was severely hindered by the binding effect of metaplast. In contrast, rotary kiln pyrolysis facilitated a greater distribution proportion of HTEs components into pulverization char at lower temperatures. Under optimal conditions, the distribution of As, Pb, and Cr into pulverization char surpassed 70 %. The strengthening thermal fragmentation in the rotary kiln reduce the binding effects, effectively increasing the distribution of copper-rich components into pulverized char.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106883"},"PeriodicalIF":5.8,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747817","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-26DOI: 10.1016/j.jaap.2024.106879
Han Jiang , Lichao Ge , Hongcui Feng , Chunyao Xu , Qingyuan Yang , Xinkai Li , Xin Liu , Yang Wang , Chang Xu
The effects of thermal recovery technology on the composite carbon fiber beams from wind turbine blades were investigated. Nonisothermal thermogravimetric experiments performed under different atmospheres showed that the reaction activation energy were the smallest for N2, and Δm was approximately 21.64 %. The activation energy was largest in air. The activation energies of the nonisothermal reactions at heating rates of 5, 10, and 15 °C/min in N2 were 93.43, 116.95 and 128.86 kJ/mol, respectively. Higher heating rates led to more difficult reactions. The compositions of the products formed during isothermal pyrolysis at 600 °C were analyzed. CO2 was the main component of gaseous products; and the remaining components were small combustible gases. The gas products accounted for 4.58 % of the total yield. The liquid tar product was approximately 21.28 %, featuring mostly aromatic substances containing arene rings, similar to phenol. The solid products accounted for approximately 74.14 % of the weight of the original reactant. The reaction mechanism was analyzed; the reaction predominantly involved the resin component of the composite, and the recovered carbon fibers remained essentially unchanged after the reaction. These results showed that it is feasible to recover carbon fibers from wind turbine blade composite carbon fiber beams by pyrolysis.
{"title":"Thermal transformations during thermal recovery of end-of-life composite carbon fiber beams from wind turbine blades","authors":"Han Jiang , Lichao Ge , Hongcui Feng , Chunyao Xu , Qingyuan Yang , Xinkai Li , Xin Liu , Yang Wang , Chang Xu","doi":"10.1016/j.jaap.2024.106879","DOIUrl":"10.1016/j.jaap.2024.106879","url":null,"abstract":"<div><div>The effects of thermal recovery technology on the composite carbon fiber beams from wind turbine blades were investigated. Nonisothermal thermogravimetric experiments performed under different atmospheres showed that the reaction activation energy were the smallest for N<sub>2</sub>, and Δm was approximately 21.64 %. The activation energy was largest in air. The activation energies of the nonisothermal reactions at heating rates of 5, 10, and 15 °C/min in N<sub>2</sub> were 93.43, 116.95 and 128.86 kJ/mol, respectively. Higher heating rates led to more difficult reactions. The compositions of the products formed during isothermal pyrolysis at 600 °C were analyzed. CO<sub>2</sub> was the main component of gaseous products; and the remaining components were small combustible gases. The gas products accounted for 4.58 % of the total yield. The liquid tar product was approximately 21.28 %, featuring mostly aromatic substances containing arene rings, similar to phenol. The solid products accounted for approximately 74.14 % of the weight of the original reactant. The reaction mechanism was analyzed; the reaction predominantly involved the resin component of the composite, and the recovered carbon fibers remained essentially unchanged after the reaction. These results showed that it is feasible to recover carbon fibers from wind turbine blade composite carbon fiber beams by pyrolysis.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"185 ","pages":"Article 106879"},"PeriodicalIF":5.8,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142744416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-26DOI: 10.1016/j.jaap.2024.106880
Samy Yousef , Justas Eimontas , Nerijus Striūgas , Marius Praspaliauskas , Mohammed Ali Abdelnaby
This research aims to study the pyrolysis behavior of old buttons (main non-textile components) and their kinetic behavior to convert them into energy and their original chemical compounds. The pyrolysis experiments were performed using a thermogravimetric analyzer (TG) on buttons have different composition that were defined using FTIR, elemental and proximate analysis. The composition of the valuable chemicals generated from the pyrolysis process were observed TG-FTIR and GC/MS. The kinetic parameters of the decomposition process were also studied using conventional modeling methods and artificial neural network (ANN) as an advanced machine learning tool. The results showed that polyester, nylon and their blends are the most commonly used materials in button manufacturing. The physical analysis showed that the buttons are very rich in volatile matter content (92.08–99.67 wt%) and completely decompose up to 490 °C at 92–100 wt%. Meanwhile, GC/MS showed that the pyrolysis vapors released from polyester buttons were rich in styrene (84.54 %), while caprolactam (40.30 %) was the dominant compound in nylon buttons versus naphthalene, 1,2,3,4-tetrahydro-2-phenyl- (67.71 %) was the major compound in the mixture sample. The kinetic analysis showed that the activation energy of the degradation process was in the ranges of 152–202 kJ/mol (polyester), 156–201 kJ/mol (nylon), 402–449 kJ/mol (mixed) and the ANN model was successfully trained and predicted the degradation regions of the buttons. Accordingly, pyrolysis of buttons is highly recommended to valorize buttons and convert them into parent chemical compounds.
{"title":"Pyrolysis behavior of non-textile components (buttons) and their kinetic analysis using artificial neural network","authors":"Samy Yousef , Justas Eimontas , Nerijus Striūgas , Marius Praspaliauskas , Mohammed Ali Abdelnaby","doi":"10.1016/j.jaap.2024.106880","DOIUrl":"10.1016/j.jaap.2024.106880","url":null,"abstract":"<div><div>This research aims to study the pyrolysis behavior of old buttons (main non-textile components) and their kinetic behavior to convert them into energy and their original chemical compounds. The pyrolysis experiments were performed using a thermogravimetric analyzer (TG) on buttons have different composition that were defined using FTIR, elemental and proximate analysis. The composition of the valuable chemicals generated from the pyrolysis process were observed TG-FTIR and GC/MS. The kinetic parameters of the decomposition process were also studied using conventional modeling methods and artificial neural network (ANN) as an advanced machine learning tool. The results showed that polyester, nylon and their blends are the most commonly used materials in button manufacturing. The physical analysis showed that the buttons are very rich in volatile matter content (92.08–99.67 wt%) and completely decompose up to 490 °C at 92–100 wt%. Meanwhile, GC/MS showed that the pyrolysis vapors released from polyester buttons were rich in styrene (84.54 %), while caprolactam (40.30 %) was the dominant compound in nylon buttons versus naphthalene, 1,2,3,4-tetrahydro-2-phenyl- (67.71 %) was the major compound in the mixture sample. The kinetic analysis showed that the activation energy of the degradation process was in the ranges of 152–202 kJ/mol (polyester), 156–201 kJ/mol (nylon), 402–449 kJ/mol (mixed) and the ANN model was successfully trained and predicted the degradation regions of the buttons. Accordingly, pyrolysis of buttons is highly recommended to valorize buttons and convert them into parent chemical compounds.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106880"},"PeriodicalIF":5.8,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-26DOI: 10.1016/j.jaap.2024.106877
Shan Cheng , Yi Fu , Hong Tian , Yi Cheng , Jiawei Wang , Jiang Zhu , Linxi Guo , Xuan Huang
The selectivity and catalytic mechanism of HZSM-5 in the pyrolysis of lignin model compounds at 600 °C were investigated using Py-GC/MS and density functional theory (DFT). The findings indicate that HZSM-5 elevated the relative content of aromatic hydrocarbons in the pyrolysis products of phenol, vanillin, and syringol by 12.3 %, 11.7 %, and 7.5 %, respectively. Meanwhile, the relative content of oxygen-containing products, including aldehydes and acids, was reduced by 15.7–52.0 %. Throughout the pyrolysis of lignin model compounds, various side chain reactions take place, such as dissociation, decarbonylation, isomerization rearrangement, alkylation, and aromatization. The selective catalytic decomposition mechanism of HZSM-5 on oxygen-containing functional groups involves both the physical selection imparted by the pore size structure and the selection of acid sites that form hydrogen bonds with hydroxyl, carbonyl, and methoxy groups. This mechanism was corroborated by DFT calculations, which showed that the energy barriers for the removal of most oxygen-containing functional groups were lowered by 1.7–72.4 kJ/mol. These results provide an in-depth understanding of the catalytic pyrolysis of lignin and pave the way for future research on the high-value utilization of waste lignin.
{"title":"Aromatic-enriched bio-oil from lignin pyrolysis catalyzed by HZSM-5: Insights into product selectivity and in-situ deoxygenation mechanism","authors":"Shan Cheng , Yi Fu , Hong Tian , Yi Cheng , Jiawei Wang , Jiang Zhu , Linxi Guo , Xuan Huang","doi":"10.1016/j.jaap.2024.106877","DOIUrl":"10.1016/j.jaap.2024.106877","url":null,"abstract":"<div><div>The selectivity and catalytic mechanism of HZSM-5 in the pyrolysis of lignin model compounds at 600 °C were investigated using Py-GC/MS and density functional theory (DFT). The findings indicate that HZSM-5 elevated the relative content of aromatic hydrocarbons in the pyrolysis products of phenol, vanillin, and syringol by 12.3 %, 11.7 %, and 7.5 %, respectively. Meanwhile, the relative content of oxygen-containing products, including aldehydes and acids, was reduced by 15.7–52.0 %. Throughout the pyrolysis of lignin model compounds, various side chain reactions take place, such as dissociation, decarbonylation, isomerization rearrangement, alkylation, and aromatization. The selective catalytic decomposition mechanism of HZSM-5 on oxygen-containing functional groups involves both the physical selection imparted by the pore size structure and the selection of acid sites that form hydrogen bonds with hydroxyl, carbonyl, and methoxy groups. This mechanism was corroborated by DFT calculations, which showed that the energy barriers for the removal of most oxygen-containing functional groups were lowered by 1.7–72.4 kJ/mol. These results provide an in-depth understanding of the catalytic pyrolysis of lignin and pave the way for future research on the high-value utilization of waste lignin.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"185 ","pages":"Article 106877"},"PeriodicalIF":5.8,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142721075","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-24DOI: 10.1016/j.jaap.2024.106882
Grazielle Emanuella de Souza dos Santos, Cassiano Cunha Oliveira, Lucas Gomes Moura, Carla Eponina Hori, Marcos Antonio de Souza Barrozo
This study investigates the impact of calcium oxide (CaO) and niobium oxide (Nb2O5) catalysts on the analytical pyrolysis of brewer's spent grain (BSG) at temperatures of 550, 650 and 750 °C. The results demonstrate that CaO and Nb2O5 based catalysts reduced oxygenated compounds and enhanced the formation of lighter hydrocarbons. At 550 °C, the hydrocarbon relative yield increased from 2.4 % under non-catalytic conditions to 18 % with FeCaO catalyst. The inclusion of iron in the catalysts contributed to improved vapor quality and stability, leading to superior hydrocarbon conversion rates. An increase in hydrocarbon production was observed across all catalysts at various pyrolysis temperatures. Regarding oxygenated compounds, catalytic tests at 650 °C and 750 °C resulted in a slight decrease in oxygenate relative yields, with Nb2O5 exhibiting the most significant reduction, dropping from 59 % to 44 % and from 56 % to 40 %, respectively, compared to non-catalytic conditions. Conversely, at 550 °C, the catalyst's impact on oxygenate relative yields was minimal. A comparison between catalytic and non-catalytic tests at 550 °C revealed a reduction in the relative yield of oxygenated compounds with three or more oxygen atoms, from 32 % to below 12 %, while compounds containing one oxygen atom increased from 2 % to 31 % when using FeCaO catalyst. This trend persisted across all catalytic conditions, suggesting partial deoxygenation of oxygenated compounds. Increasing the pyrolysis temperature consistently contributed to deoxygenation across all catalysts. These findings contribute to the advancement of bio-oil production technologies from biomass resources.
本研究调查了氧化钙（CaO）和氧化铌（Nb2O5）催化剂在 550、650 和 750 °C 温度下对啤酒糟（BSG）分析热解的影响。结果表明，基于 CaO 和 Nb2O5 的催化剂减少了含氧化合物，并促进了轻质碳氢化合物的形成。550 °C 时，碳氢化合物的相对产率从非催化条件下的 2.4% 提高到 FeCaO 催化剂条件下的 18%。在催化剂中加入铁有助于提高蒸汽质量和稳定性，从而提高碳氢化合物的转化率。在不同的热解温度下，所有催化剂的碳氢化合物产量都有所增加。在含氧化合物方面，650 ℃ 和 750 ℃ 的催化试验导致含氧化合物的相对产量略有下降，其中 Nb2O5 的降幅最大，与非催化条件相比，分别从 59% 降至 44%，从 56% 降至 40%。相反，在 550 °C 条件下，催化剂对含氧化合物相对产率的影响很小。通过比较 550 °C 下的催化和非催化试验发现，使用 FeCaO 催化剂时，含三个或更多氧原子的含氧化合物的相对产率从 32% 降至 12% 以下，而含一个氧原子的化合物则从 2% 增加到 31%。这种趋势在所有催化条件下都持续存在，表明含氧化合物部分脱氧。在所有催化剂中，提高热解温度始终有助于脱氧。这些发现有助于促进生物质资源生物油生产技术的发展。
{"title":"From brewers’ waste to fuel precursors: Catalytic pyrolysis of BSG using CaO and Nb2O5-based catalysts for enhanced hydrocarbon production","authors":"Grazielle Emanuella de Souza dos Santos, Cassiano Cunha Oliveira, Lucas Gomes Moura, Carla Eponina Hori, Marcos Antonio de Souza Barrozo","doi":"10.1016/j.jaap.2024.106882","DOIUrl":"10.1016/j.jaap.2024.106882","url":null,"abstract":"<div><div>This study investigates the impact of calcium oxide (CaO) and niobium oxide (Nb<sub>2</sub>O<sub>5</sub>) catalysts on the analytical pyrolysis of brewer's spent grain (BSG) at temperatures of 550, 650 and 750 °C. The results demonstrate that CaO and Nb<sub>2</sub>O<sub>5</sub> based catalysts reduced oxygenated compounds and enhanced the formation of lighter hydrocarbons. At 550 °C, the hydrocarbon relative yield increased from 2.4 % under non-catalytic conditions to 18 % with FeCaO catalyst. The inclusion of iron in the catalysts contributed to improved vapor quality and stability, leading to superior hydrocarbon conversion rates. An increase in hydrocarbon production was observed across all catalysts at various pyrolysis temperatures. Regarding oxygenated compounds, catalytic tests at 650 °C and 750 °C resulted in a slight decrease in oxygenate relative yields, with Nb<sub>2</sub>O<sub>5</sub> exhibiting the most significant reduction, dropping from 59 % to 44 % and from 56 % to 40 %, respectively, compared to non-catalytic conditions. Conversely, at 550 °C, the catalyst's impact on oxygenate relative yields was minimal. A comparison between catalytic and non-catalytic tests at 550 °C revealed a reduction in the relative yield of oxygenated compounds with three or more oxygen atoms, from 32 % to below 12 %, while compounds containing one oxygen atom increased from 2 % to 31 % when using FeCaO catalyst. This trend persisted across all catalytic conditions, suggesting partial deoxygenation of oxygenated compounds. Increasing the pyrolysis temperature consistently contributed to deoxygenation across all catalysts. These findings contribute to the advancement of bio-oil production technologies from biomass resources.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"185 ","pages":"Article 106882"},"PeriodicalIF":5.8,"publicationDate":"2024-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142721076","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}
Aluminum cans are typical solid waste. Polyester coatings not only polluted the environment, but also affected the quality of aluminum recycling. In this study, three common local polyester coatings on the surface of aluminum cans were selected as raw materials (PC-PB, PC-VY and PC-SG). Thermogravimetric analysis, elemental analysis, Fourier transform infrared spectrometer and pyrolysis gas chromatography/mass spectrometry (PY-GC/MS) were used to study the pyrolysis behavior and pyrolysis products of the polymer components coated on the aluminum cans. TG analysis showed that pyrolysis of the coatings mainly occurred at 250–540 °C, with a weight loss of about 25 % for the polyester coating PC-PB and PC-VG, and a lower weight loss of 15 % for polyester coating PC-SY. The effect of pyrolysis temperature on the pyrolysis products of polyester coatings was investigated using PY-GC/MS. The results showed that the main products of pyrolysis included four major groups: oxygenated compounds, aromatic compounds, nitrogenous compounds and aliphatic hydrocarbons. At 600 °C, the aromatic compounds, oxide-containing reached 57–67 % and 20–27 %, respectively. The main pyrolysis products include neopentyl glycol, phthalic anhydride, toluene, styrene and so on. The high content of aromatic compounds in the product can be used as chemical raw materials as well as alternative fuels. In addition, the pyrolysis principles of the three main components of polyester coatings (polyester resins, amino resins, and styrene-acrylic resins) were postulated.
{"title":"Investigation in the pyrolysis of polyester coated on aluminum-based beverage: Thermodynamic properties, product and mechanism","authors":"Zhen-Qiang Yu , Guo-Dong Hong , Wei Zhao , Dong Liang , Zhen Huang , Che Zhao , Rui Shan , Hao-Ran Yuan , Yong Chen","doi":"10.1016/j.jaap.2024.106878","DOIUrl":"10.1016/j.jaap.2024.106878","url":null,"abstract":"<div><div>Aluminum cans are typical solid waste. Polyester coatings not only polluted the environment, but also affected the quality of aluminum recycling. In this study, three common local polyester coatings on the surface of aluminum cans were selected as raw materials (PC-PB, PC-VY and PC-SG). Thermogravimetric analysis, elemental analysis, Fourier transform infrared spectrometer and pyrolysis gas chromatography/mass spectrometry (PY-GC/MS) were used to study the pyrolysis behavior and pyrolysis products of the polymer components coated on the aluminum cans. TG analysis showed that pyrolysis of the coatings mainly occurred at 250–540 °C, with a weight loss of about 25 % for the polyester coating PC-PB and PC-VG, and a lower weight loss of 15 % for polyester coating PC-SY. The effect of pyrolysis temperature on the pyrolysis products of polyester coatings was investigated using PY-GC/MS. The results showed that the main products of pyrolysis included four major groups: oxygenated compounds, aromatic compounds, nitrogenous compounds and aliphatic hydrocarbons. At 600 °C, the aromatic compounds, oxide-containing reached 57–67 % and 20–27 %, respectively. The main pyrolysis products include neopentyl glycol, phthalic anhydride, toluene, styrene and so on. The high content of aromatic compounds in the product can be used as chemical raw materials as well as alternative fuels. In addition, the pyrolysis principles of the three main components of polyester coatings (polyester resins, amino resins, and styrene-acrylic resins) were postulated.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"185 ","pages":"Article 106878"},"PeriodicalIF":5.8,"publicationDate":"2024-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142744708","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-22DOI: 10.1016/j.jaap.2024.106874
Guilherme Quintela Calixto , Josué da Cruz de Souza , José Luiz Francisco Alves , Joemil Oliveira de Deus Junior , Júlio de Andrade Oliveira Marques , Iane Maiara Soares de Souza , Sibele Berenice Castellã Pergher , Dulce Maria de Araújo Melo , Renata Martins Braga
Developing biofuels with characteristics similar to current fossil fuels and compatibility with existing petroleum infrastructure (drop-in biofuels) is gaining prominence, aligning with global efforts towards carbon-neutral economies and decarbonization of the transportation sector. The originality of the current study involves two directions: first, the use of Chlorella sp. microalgae, cultivated under simulated post-combustion gas, as a raw material for producing drop-in biofuel precursors; and second, an investigation of the catalytic activity of hierarchical zeolites in the deoxygenation and denitrogenation of volatile pyrolysis products, enhancing hydrocarbon content. To accomplish this, a micro-furnace-type temperature-programmable pyrolyzer coupled with chromatographic separation and mass spectrometry detection (Py-GC/MS) was utilized to assess the upgrading effectiveness of distinct zeolites (faujasite-type, MFI-type, and mordenite-type) on volatile pyrolysis products. All tested zeolites effectively reduced oxygenated and nitrogenated compounds in the volatile pyrolysis products, enhancing their suitability for producing renewable fuel. This supports sustainable development goals by promoting affordable, clean energy and climate action. HMor yielded the highest hydrocarbon content (98.5 %), followed by HZSM-5 (97.6 %) and HY (85.5 %). Catalytic upgrading significantly increased the concentration of aromatic hydrocarbons (at least 66.3 %), with MFI-type zeolites showing the highest selectivity for valuable BETX compounds (benzene, ethylbenzene, toluene, xylene). Hydrocarbons in the gasoline range, with up to 91.7 %, predominantly align with the needs of the transportation fuel market. The principal component analysis illustrates that using MFI-type zeolites promoted the lowest selectivity for PAHs, constituting precursors for coke formation, which is advantageous for ensuring a longer catalyst lifespan. Our results are promising and encourage the conversion of microalgal biomass into renewable fuel additives for formulating drop-in biofuels, as hydrocarbon-rich volatile pyrolysis products could be directly integrated into existing biorefineries. Thus, microalgal biomass cultivated using flue gas as the carbon source can be viewed as a versatile and promising resource for producing renewable fuel additives, contributing to developing a sustainable, low-carbon future.
{"title":"Catalyst screening for conversion of Chlorella sp. to aromatic fuel additives: A sustainable strategy for CO2 capture","authors":"Guilherme Quintela Calixto , Josué da Cruz de Souza , José Luiz Francisco Alves , Joemil Oliveira de Deus Junior , Júlio de Andrade Oliveira Marques , Iane Maiara Soares de Souza , Sibele Berenice Castellã Pergher , Dulce Maria de Araújo Melo , Renata Martins Braga","doi":"10.1016/j.jaap.2024.106874","DOIUrl":"10.1016/j.jaap.2024.106874","url":null,"abstract":"<div><div>Developing biofuels with characteristics similar to current fossil fuels and compatibility with existing petroleum infrastructure (drop-in biofuels) is gaining prominence, aligning with global efforts towards carbon-neutral economies and decarbonization of the transportation sector. The originality of the current study involves two directions: first, the use of <em>Chlorella</em> sp. microalgae, cultivated under simulated post-combustion gas, as a raw material for producing drop-in biofuel precursors; and second, an investigation of the catalytic activity of hierarchical zeolites in the deoxygenation and denitrogenation of volatile pyrolysis products, enhancing hydrocarbon content. To accomplish this, a micro-furnace-type temperature-programmable pyrolyzer coupled with chromatographic separation and mass spectrometry detection (Py-GC/MS) was utilized to assess the upgrading effectiveness of distinct zeolites (faujasite-type, MFI-type, and mordenite-type) on volatile pyrolysis products. All tested zeolites effectively reduced oxygenated and nitrogenated compounds in the volatile pyrolysis products, enhancing their suitability for producing renewable fuel. This supports sustainable development goals by promoting affordable, clean energy and climate action. HMor yielded the highest hydrocarbon content (98.5 %), followed by HZSM-5 (97.6 %) and HY (85.5 %). Catalytic upgrading significantly increased the concentration of aromatic hydrocarbons (at least 66.3 %), with MFI-type zeolites showing the highest selectivity for valuable BETX compounds (benzene, ethylbenzene, toluene, xylene). Hydrocarbons in the gasoline range, with up to 91.7 %, predominantly align with the needs of the transportation fuel market. The principal component analysis illustrates that using MFI-type zeolites promoted the lowest selectivity for PAHs, constituting precursors for coke formation, which is advantageous for ensuring a longer catalyst lifespan. Our results are promising and encourage the conversion of microalgal biomass into renewable fuel additives for formulating drop-in biofuels, as hydrocarbon-rich volatile pyrolysis products could be directly integrated into existing biorefineries. Thus, microalgal biomass cultivated using flue gas as the carbon source can be viewed as a versatile and promising resource for producing renewable fuel additives, contributing to developing a sustainable, low-carbon future.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"185 ","pages":"Article 106874"},"PeriodicalIF":5.8,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142744607","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-22DOI: 10.1016/j.jaap.2024.106876
Jamiu Mosebolatan Jabar , Matthew Ayorinde Adebayo , Tella Adewale Akanni Taleat , Murat Yılmaz , Selvasembian Rangabhashiyam
The industrial sector of textile effluent discharge comprised majorly of toxic pollutants of synthetic dyes. Lignocellulosic based biomass is a potential precursor for the preparation of biochar type adsorbent for treating wastewater. The present research examined the leaf of Ipoma batatas in the synthesis and application of biochar in the adsorptive removal of procion orange MX-2R (PO) from aqueous solution. The Ipoma batatas biochar (IBB) was prepared from the treatment of Ipoma batatas leaf (IBL) biomass with CaCl2, further activation using microwave-assisted electromagnetic radiation and pyrolysis approach. The batch adsorption assessments of the process parameters were performed with the range of experimental conditions such as initial PO concentration of 1.0–70.0 mg/L, adsorption contact time up to 240 min, solution pH 1.0–11.0, IBL/IBB dosage 0.05–0.30 g/L and adsorption temperature of 303–333 K. The total surface area of IBB exhibited high value of 1175.47 m2/g compared to that of IBL surface area 439.25 m2/g. The equilibrium model analysis showed the adsorption capacity according to Liu model presents 221.20 mg/g (IBL) and 750.80 mg/g (IBB). This study showed the potential of IBB over IBL towards the adsorptive removal of PO from simulated solution.
{"title":"Ipoma batatas (sweet potato) leaf and leaf-based biochar as potential adsorbents for procion orange MX-2R removal from aqueous solution","authors":"Jamiu Mosebolatan Jabar , Matthew Ayorinde Adebayo , Tella Adewale Akanni Taleat , Murat Yılmaz , Selvasembian Rangabhashiyam","doi":"10.1016/j.jaap.2024.106876","DOIUrl":"10.1016/j.jaap.2024.106876","url":null,"abstract":"<div><div>The industrial sector of textile effluent discharge comprised majorly of toxic pollutants of synthetic dyes. Lignocellulosic based biomass is a potential precursor for the preparation of biochar type adsorbent for treating wastewater. The present research examined the leaf of <em>Ipoma batatas</em> in the synthesis and application of biochar in the adsorptive removal of procion orange MX-2R (PO) from aqueous solution. The <em>Ipoma batatas</em> biochar (IBB) was prepared from the treatment of <em>Ipoma batatas</em> leaf (IBL) biomass with CaCl<sub>2</sub>, further activation using microwave-assisted electromagnetic radiation and pyrolysis approach. The batch adsorption assessments of the process parameters were performed with the range of experimental conditions such as initial PO concentration of 1.0–70.0 mg/L, adsorption contact time up to 240 min, solution pH 1.0–11.0, IBL/IBB dosage 0.05–0.30 g/L and adsorption temperature of 303–333 K. The total surface area of IBB exhibited high value of 1175.47 m<sup>2</sup>/g compared to that of IBL surface area 439.25 m<sup>2</sup>/g. The equilibrium model analysis showed the adsorption capacity according to Liu model presents 221.20 mg/g (IBL) and 750.80 mg/g (IBB). This study showed the potential of IBB over IBL towards the adsorptive removal of PO from simulated solution.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"185 ","pages":"Article 106876"},"PeriodicalIF":5.8,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142701170","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-22DOI: 10.1016/j.jaap.2024.106873
Chenyang Liu , Zhongjie Shen , Haigang Zhang , Guinan He , Weifeng Li , Haifeng Liu
Co-pyrolysis of sewage sludge (SS) and low rank bituminous coal (BC) was considered as an effective technology in realising the co-resource utilization and disposal of municipal waste. The current work focused on the co-pyrolysis characteristics and synergistic mechanisms under rapid/slow heating conditions, with experimental and analytical methods of the thermogravimetric-mass spectrometry (TG-MS), gas chromatography (GC), and Fourier transform infrared spectroscopy (FTIR). The results showed that the heating rate and mixing ratio of SS and BC caused different yields of the co-pyrolysis products. The gas products performed different releasing rules with the effect of mixing ratio of SS and BC, and the different stages during the slow pyrolysis were defined in terms of weight loss and product release. Under the rapid heating condition, the gas product yield in the experiment was found to be consistently higher than the theoretical yield, regardless of the mixing ratio. The addition of SS in the mixtures would increase the yield content of CO2 and high calorific gases (C2H2, C2H4, C2H6) and reduce H2, CO, and CH4. The intensities and widths of the absorption peaks of functional groups such as O-H, C-H, C=O and C=C in the char decreased. The morphology, pore structure, and particle size distribution of the pyrolyzed samples were compared and analysed. Kinetic analysis was carried out according to different stages of slow pyrolysis. Finally, the synergistic effect and mechanism of the co-pyrolysis were comprehensively compared and revealed under slow/rapid heating conditions.
污水污泥（SS）和低级烟煤（BC）的协同热解被认为是实现城市垃圾资源化利用和处置的有效技术。本研究采用热重质谱法（TG-MS）、气相色谱法（GC）和傅立叶变换红外光谱法（FTIR）等实验和分析方法，重点研究了快速/慢速加热条件下的协同热解特性和协同机理。结果表明，SS 和 BC 的加热速率和混合比例会导致共热解产物的产量不同。气体产物随 SS 和 BC 混合比的变化而表现出不同的释放规律，并从重量损失和产物释放的角度定义了缓慢热解过程中的不同阶段。实验发现，在快速加热条件下，无论混合比如何，气体产物产率始终高于理论产率。在混合物中加入 SS 会增加 CO2 和高热量气体（C2H2、C2H4、C2H6）的产率，减少 H2、CO 和 CH4 的产率。炭中 O-H、C-H、C=O 和 C=C 等官能团吸收峰的强度和宽度都有所下降。对热解样品的形态、孔隙结构和粒度分布进行了比较和分析。根据缓慢热解的不同阶段进行了动力学分析。最后，综合比较并揭示了在慢速/快速加热条件下协同热解的协同效应和机理。
{"title":"Comprehensive study on co-pyrolysis mechanisms of sewage sludge and low rank coal under rapid/slow heating conditions","authors":"Chenyang Liu , Zhongjie Shen , Haigang Zhang , Guinan He , Weifeng Li , Haifeng Liu","doi":"10.1016/j.jaap.2024.106873","DOIUrl":"10.1016/j.jaap.2024.106873","url":null,"abstract":"<div><div>Co-pyrolysis of sewage sludge (SS) and low rank bituminous coal (BC) was considered as an effective technology in realising the co-resource utilization and disposal of municipal waste. The current work focused on the co-pyrolysis characteristics and synergistic mechanisms under rapid/slow heating conditions, with experimental and analytical methods of the thermogravimetric-mass spectrometry (TG-MS), gas chromatography (GC), and Fourier transform infrared spectroscopy (FTIR). The results showed that the heating rate and mixing ratio of SS and BC caused different yields of the co-pyrolysis products. The gas products performed different releasing rules with the effect of mixing ratio of SS and BC, and the different stages during the slow pyrolysis were defined in terms of weight loss and product release. Under the rapid heating condition, the gas product yield in the experiment was found to be consistently higher than the theoretical yield, regardless of the mixing ratio. The addition of SS in the mixtures would increase the yield content of CO<sub>2</sub> and high calorific gases (C<sub>2</sub>H<sub>2</sub>, C<sub>2</sub>H<sub>4</sub>, C<sub>2</sub>H<sub>6</sub>) and reduce H<sub>2</sub>, CO, and CH<sub>4</sub>. The intensities and widths of the absorption peaks of functional groups such as O-H, C-H, C=O and C=C in the char decreased. The morphology, pore structure, and particle size distribution of the pyrolyzed samples were compared and analysed. Kinetic analysis was carried out according to different stages of slow pyrolysis. Finally, the synergistic effect and mechanism of the co-pyrolysis were comprehensively compared and revealed under slow/rapid heating conditions.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"185 ","pages":"Article 106873"},"PeriodicalIF":5.8,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142721077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-22DOI: 10.1016/j.jaap.2024.106875
Heng Yu, Jingwen Wang, Zhoumei Xu, Bin Zou, Fukai Chu, Lei Song, Weizhao Hu, Yuan Hu
As an important renewable biomass material, bast fiber of crops has various application values. However, its flammable and decomposable characteristics bring challenges to its storage and practical applications. In this work, a steady-state tube furnace (SSTF) was built independently. And the pyrolysis and combustion behavior of three typical bast fibers: hemp, flax, and ramie were systematically studied. Among them, the total heat release of hemp and ramie was about 49.4 % higher than that of flax. And the average CO content of flax and ramie were 35.2 % and 39.5 % lower than hemp, respectively. Data-based fire hazard assessment illustrated that the hemp had the highest fire hazard. A Genetic Algorithm (GA)-based four-step reaction model was proposed and accurately predicted the pyrolysis process of bast fibers (Fdev≤0.016). Furthermore, the pyrolysis products of bast fibers were studied based on TG-FTIR and PY-GC-MS. On this basis, the possible production mechanism of pyrolysis products was proposed. This work will provide a reference for research on pyrolysis and combustion of biomass.
{"title":"Experimental and numerical investigation on pyrolysis and combustion behavior of biomass bast fibers: Hemp, flax and ramie fibers","authors":"Heng Yu, Jingwen Wang, Zhoumei Xu, Bin Zou, Fukai Chu, Lei Song, Weizhao Hu, Yuan Hu","doi":"10.1016/j.jaap.2024.106875","DOIUrl":"10.1016/j.jaap.2024.106875","url":null,"abstract":"<div><div>As an important renewable biomass material, bast fiber of crops has various application values. However, its flammable and decomposable characteristics bring challenges to its storage and practical applications. In this work, a steady-state tube furnace (SSTF) was built independently. And the pyrolysis and combustion behavior of three typical bast fibers: hemp, flax, and ramie were systematically studied. Among them, the total heat release of hemp and ramie was about 49.4 % higher than that of flax. And the average CO content of flax and ramie were 35.2 % and 39.5 % lower than hemp, respectively. Data-based fire hazard assessment illustrated that the hemp had the highest fire hazard. A Genetic Algorithm (GA)-based four-step reaction model was proposed and accurately predicted the pyrolysis process of bast fibers (<em>F</em><sub><em>dev</em></sub>≤0.016). Furthermore, the pyrolysis products of bast fibers were studied based on TG-FTIR and PY-GC-MS. On this basis, the possible production mechanism of pyrolysis products was proposed. This work will provide a reference for research on pyrolysis and combustion of biomass.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"185 ","pages":"Article 106875"},"PeriodicalIF":5.8,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700472","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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