Metal/biochar catalysts could be synthesized via directly subjecting biomass impregnated with metal salts to pyrolysis. The properties of biochar are intricately linked to the inherent composition of the raw material, which in turn could influence the degree of metal dispersion and its catalytic impact. The poplar sawdust and its fractioned proportion was employed for the preparation of Ni-based biochar catalysts. The work mainly focuses on the impact of lignocellulosic material with diverse compositions on the dispersion of nickel particles during the calcination-pyrolysis co-process. Given that cellulose and holocellulose constituted the majority of the material, the matching catalyst support may encourage the migration of nickel species to produce substantial amounts of particles, perhaps as a result of several reactions such as dehydration and aromatization. In contrast, the utilization of sawdust as a support demonstrated a remarkable effect in dispersing nickel particles, nickel particle size and H2 uptake were 7.0 nm and 19.8 μmol/g, respectively, while also displaying exceptional catalytic activity in the hydrogenation of vanillin, with the maximum conversion and 2-methoxy-4-methylphenol (MMP) yield of 99.7 % and 69.0 %. It has been determined that the presence of lignin in the system has a beneficial impact on the dispersion of nickel and its catalytic activity.
{"title":"Preparation of a finely dispersion nickel-based in-situ pyrolysis catalyst: Influence of lignocellulosic constituents","authors":"Weidong Ren, Yuewen Shao, Mengjiao Fan, Chao Li, Qingyin Li, Xun Hu","doi":"10.1016/j.jaap.2024.106784","DOIUrl":"10.1016/j.jaap.2024.106784","url":null,"abstract":"<div><div>Metal/biochar catalysts could be synthesized via directly subjecting biomass impregnated with metal salts to pyrolysis. The properties of biochar are intricately linked to the inherent composition of the raw material, which in turn could influence the degree of metal dispersion and its catalytic impact. The poplar sawdust and its fractioned proportion was employed for the preparation of Ni-based biochar catalysts. The work mainly focuses on the impact of lignocellulosic material with diverse compositions on the dispersion of nickel particles during the calcination-pyrolysis co-process. Given that cellulose and holocellulose constituted the majority of the material, the matching catalyst support may encourage the migration of nickel species to produce substantial amounts of particles, perhaps as a result of several reactions such as dehydration and aromatization. In contrast, the utilization of sawdust as a support demonstrated a remarkable effect in dispersing nickel particles, nickel particle size and H<sub>2</sub> uptake were 7.0 nm and 19.8 μmol/g, respectively, while also displaying exceptional catalytic activity in the hydrogenation of vanillin, with the maximum conversion and 2-methoxy-4-methylphenol (MMP) yield of 99.7 % and 69.0 %. It has been determined that the presence of lignin in the system has a beneficial impact on the dispersion of nickel and its catalytic activity.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106784"},"PeriodicalIF":5.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142319098","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 : 2024-09-23DOI: 10.1016/j.jaap.2024.106781
Gabriela Fontes Mayrinck Cupertino , Allana Katiussya Silva Pereira , João Gilberto Meza Ucella-Filho , Fabíola Martins Delatorre , Álison Moreira da Silva , Kamilla Crysllayne Alves da Silva , Elias Costa de Souza , Luciana Alves Parreira , Alexandre Santos Pimenta , Daniel Saloni , Rafael Luque , Ananias Francisco Dias Júnior
The global concern about plastic is a matter of great importance. Coprocessing biomass and polyethylene terephthalate (PET) through pyrolysis can represent a strategy to reuse these materials, transforming them into products of industrial interest. Thus, this study aims to understand the influence of the co-pyrolysis of biomass and PET on bio-oil (BO). The PET quantities used were 0 %, 15 %, and 25 % of the eucalyptus biomass dry basis. The co-pyrolysis was performed in a fixed-bed reactor in a low-oxygen atmosphere without gas entry at a final temperature of 450°C and three heating rates (1, 3, and 5°C.min−1). The liquid fraction underwent double distillation, producing purified bio-oil (BOP) with yields of 54 %, 57 %, and 55 %, respectively, influenced solely by the heating rates of 1, 3, and 5°C min−1. After purification, BOP's pH, density, and viscosity were analyzed. The chemical composition of BOP was subject to GC-MS analysis. The addition of PET and the variation in heating rate influenced the composition of the BOP produced. The liquid density decreased as the PET proportion in the biomass increased. The heating rate increase reduced BOP's pH from 2.75 to 2.61. Therefore, lower heating rates and PET proportions tend to increase the viscosity of BOP. Ketones were the most representative organic compounds in all evaluated materials, followed by phenols, furans, and pyrans.
{"title":"Prospects for the utilization of bio-oil-derived chemicals generated via co-pyrolysis of biomass and polyethylene terephthalate (PET)","authors":"Gabriela Fontes Mayrinck Cupertino , Allana Katiussya Silva Pereira , João Gilberto Meza Ucella-Filho , Fabíola Martins Delatorre , Álison Moreira da Silva , Kamilla Crysllayne Alves da Silva , Elias Costa de Souza , Luciana Alves Parreira , Alexandre Santos Pimenta , Daniel Saloni , Rafael Luque , Ananias Francisco Dias Júnior","doi":"10.1016/j.jaap.2024.106781","DOIUrl":"10.1016/j.jaap.2024.106781","url":null,"abstract":"<div><div>The global concern about plastic is a matter of great importance. Coprocessing biomass and polyethylene terephthalate (PET) through pyrolysis can represent a strategy to reuse these materials, transforming them into products of industrial interest. Thus, this study aims to understand the influence of the co-pyrolysis of biomass and PET on bio-oil (BO). The PET quantities used were 0 %, 15 %, and 25 % of the eucalyptus biomass dry basis. The co-pyrolysis was performed in a fixed-bed reactor in a low-oxygen atmosphere without gas entry at a final temperature of 450°C and three heating rates (1, 3, and 5°C.min<sup>−1</sup>). The liquid fraction underwent double distillation, producing purified bio-oil (BOP) with yields of 54 %, 57 %, and 55 %, respectively, influenced solely by the heating rates of 1, 3, and 5°C min<sup>−1</sup>. After purification, BOP's pH, density, and viscosity were analyzed. The chemical composition of BOP was subject to GC-MS analysis. The addition of PET and the variation in heating rate influenced the composition of the BOP produced. The liquid density decreased as the PET proportion in the biomass increased. The heating rate increase reduced BOP's pH from 2.75 to 2.61. Therefore, lower heating rates and PET proportions tend to increase the viscosity of BOP. Ketones were the most representative organic compounds in all evaluated materials, followed by phenols, furans, and pyrans.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106781"},"PeriodicalIF":5.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142327176","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 : 2024-09-23DOI: 10.1016/j.jaap.2024.106777
Da Cui , Bowen Zhang , Yupeng Liu , Shuang Wu , Xinmin Wang , Qing Wang , Xuehua Zhang , Moslem Fattahi , Jinghui Zhang
This study carried out co-hydrothermal carbonization (Co-HTC) on sewage sludge (SS) and sunflower straw (SFS) at various ratios (1:0, 3:1, 1:1, 1:3, 0:1) to prepare hydrochar. The raw samples and produced hydrochar were characterized using ultimate analysis, proximate analysis, Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The potential synergistic impact during the reaction process were analyzed. As the SFS ratio increased, the fuel ratio of hydrothermal carbons rose from 0.29 to 0.37, while the higher heating value (HHV) improved from 7.44 (MJ/kg) to 20.86 (MJ/kg). The co-hydrothermal synergistic effect resulted in enhanced the hydrochar yield, energy yield, carbon sequestration rate and organic retention rate. Compared to raw sample, the surface of hydrochar exhibits a rougher and more fragmented structure, with an increased number of microspheres and micropores, resulted in an increased specific surface area. Thermogravimetric analysis (TGA) demonstrated that, in comparison to HTC of sludge alone, the Co-HTC of SS with SFS enhances the ignition temperature and delays the completion of combustion. Therefore, Co-HTC with SFS is an effective method for converting SS into clean solid fuel for energy applications.
{"title":"Hydrochar from co-hydrothermal carbonization of sewage sludge and sunflower stover: Synergistic effects and combustion characteristics","authors":"Da Cui , Bowen Zhang , Yupeng Liu , Shuang Wu , Xinmin Wang , Qing Wang , Xuehua Zhang , Moslem Fattahi , Jinghui Zhang","doi":"10.1016/j.jaap.2024.106777","DOIUrl":"10.1016/j.jaap.2024.106777","url":null,"abstract":"<div><div>This study carried out co-hydrothermal carbonization (Co-HTC) on sewage sludge (SS) and sunflower straw (SFS) at various ratios (1:0, 3:1, 1:1, 1:3, 0:1) to prepare hydrochar. The raw samples and produced hydrochar were characterized using ultimate analysis, proximate analysis, Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The potential synergistic impact during the reaction process were analyzed. As the SFS ratio increased, the fuel ratio of hydrothermal carbons rose from 0.29 to 0.37, while the higher heating value (HHV) improved from 7.44 (MJ/kg) to 20.86 (MJ/kg). The co-hydrothermal synergistic effect resulted in enhanced the hydrochar yield, energy yield, carbon sequestration rate and organic retention rate. Compared to raw sample, the surface of hydrochar exhibits a rougher and more fragmented structure, with an increased number of microspheres and micropores, resulted in an increased specific surface area. Thermogravimetric analysis (TGA) demonstrated that, in comparison to HTC of sludge alone, the Co-HTC of SS with SFS enhances the ignition temperature and delays the completion of combustion. Therefore, Co-HTC with SFS is an effective method for converting SS into clean solid fuel for energy applications.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106777"},"PeriodicalIF":5.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142314527","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 : 2024-09-23DOI: 10.1016/j.jaap.2024.106774
Mingzhou Li , Wei Wang , Jie Yu
Three types of plastics—polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS), and PC/ABS blend—were studied in this work. Kinetic analyses were performed using the Flynn-Wall-Ozawa (FWO) and Kissinger–Akahira–Sunose (KAS) methods. The evolved volatiles during the pyrolysis of each material were analyzed, and the pyrolysis behavior was proposed using in-situ tools such as thermogravimetric analyzer-Fourier transform infrared spectroscopic (TG-FTIR) and gas chromatographic separation and mass spectrometry detection (Py-GC/MS). The three samples were also pyrolysed in a fixed bed reactor to elucidate the impact of secondary reaction. For PC, the activation energy increases as the reaction progresses. PC primarily generated CO2 and oxygenated compounds. For ABS, the activation energy experienced a slight decrease once the depolymerization reaction initiates, while a reversed trend can be observed at higher conversion rates. ABS pyrolysis mainly produced nitrogen-containing compounds and mono-aromatics. In the case of PC/ABS blend, a distinctive two-stage decomposition mechanism was observed. The interaction between PC and ABS in the blend promoted the formation of N/O-containing compounds. Additionally, this interaction enhanced the production of lighter phenols at the expense of bisphenol A, while ABS was not affected markedly. Stronger re-condensation and cracking reactions in the fixed bed system, facilitated the formation of poly-aromatics and lighter phenols (p-cresol and 4-ethylphenol) at the expense of bisphenol A during the pyrolysis of PC. In contrast, styrene from ABS decomposition was weakly affected by the secondary reaction. The intensified secondary reactions occurring the sample bed of the fixed bed experiments can also enhance the interaction between volatiles from ABS and PC, forming more heterocyclic N-compounds.
这项工作研究了三种塑料--聚碳酸酯（PC）、丙烯腈-丁二烯-苯乙烯（ABS）和 PC/ABS 混合物。采用 Flynn-Wall-Ozawa (FWO) 和 Kissinger-Akahira-Sunose (KAS) 方法进行了动力学分析。分析了每种材料在热解过程中挥发出来的物质，并利用热重分析仪-傅立叶变换红外光谱法（TG-FTIR）和气相色谱分离与质谱检测法（Py-GC/MS）等原位工具对热解行为提出了建议。这三种样品还在固定床反应器中进行了热解，以阐明二次反应的影响。对于 PC 来说，活化能随着反应的进行而增加。PC 主要生成二氧化碳和含氧化合物。对于 ABS 来说，一旦解聚反应开始，活化能就会略有下降，而在转化率较高时，则会出现相反的趋势。ABS 高温分解主要产生含氮化合物和单芳烃。在 PC/ABS 混合物中，观察到一种独特的两阶段分解机制。混合物中 PC 和 ABS 之间的相互作用促进了含 N/O 化合物的形成。此外，这种相互作用以牺牲双酚 A 为代价，促进了较轻酚的生成，而 ABS 则没有受到明显影响。在 PC 的热解过程中，固定床系统中较强的再缩合和裂解反应促进了多芳烃和较轻苯酚（对甲酚和 4-乙基苯酚）的形成，而双酚 A 则受到了影响。相比之下，ABS 分解产生的苯乙烯受二次反应的影响较小。在固定床实验中，样品床发生的二次反应加剧，也会增强 ABS 和 PC 挥发物之间的相互作用，形成更多的杂环 N 化合物。
{"title":"Comparison of the pyrolysis behavior of PC, ABS and PC/ABS","authors":"Mingzhou Li , Wei Wang , Jie Yu","doi":"10.1016/j.jaap.2024.106774","DOIUrl":"10.1016/j.jaap.2024.106774","url":null,"abstract":"<div><div>Three types of plastics—polycarbonate (PC), acrylonitrile-butadiene-styrene (ABS), and PC/ABS blend—were studied in this work. Kinetic analyses were performed using the Flynn-Wall-Ozawa (FWO) and Kissinger–Akahira–Sunose (KAS) methods. The evolved volatiles during the pyrolysis of each material were analyzed, and the pyrolysis behavior was proposed using in-situ tools such as thermogravimetric analyzer-Fourier transform infrared spectroscopic (TG-FTIR) and gas chromatographic separation and mass spectrometry detection (Py-GC/MS). The three samples were also pyrolysed in a fixed bed reactor to elucidate the impact of secondary reaction. For PC, the activation energy increases as the reaction progresses. PC primarily generated CO<sub>2</sub> and oxygenated compounds. For ABS, the activation energy experienced a slight decrease once the depolymerization reaction initiates, while a reversed trend can be observed at higher conversion rates. ABS pyrolysis mainly produced nitrogen-containing compounds and mono-aromatics. In the case of PC/ABS blend, a distinctive two-stage decomposition mechanism was observed. The interaction between PC and ABS in the blend promoted the formation of N/O-containing compounds. Additionally, this interaction enhanced the production of lighter phenols at the expense of bisphenol A, while ABS was not affected markedly. Stronger re-condensation and cracking reactions in the fixed bed system, facilitated the formation of poly-aromatics and lighter phenols (p-cresol and 4-ethylphenol) at the expense of bisphenol A during the pyrolysis of PC. In contrast, styrene from ABS decomposition was weakly affected by the secondary reaction. The intensified secondary reactions occurring the sample bed of the fixed bed experiments can also enhance the interaction between volatiles from ABS and PC, forming more heterocyclic N-compounds.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106774"},"PeriodicalIF":5.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142322569","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 : 2024-09-23DOI: 10.1016/j.jaap.2024.106780
Qi Niu , Xin Du , Kai Li , Qiang Lu , Wolter Prins , Frederik Ronsse
The protein-rich defatted microalgae (Nannochloropsis gaditana) after lipid extraction was used as feedstock in catalytic pyrolysis to optimize economic returns of microalgae waste utilization. The effects of Ni- and Co-modified HZSM-5 on the formation of aromatic hydrocarbons (AHs), deoxygenation and denitrogenation in catalytic fast pyrolysis were studied via pyrolysis-gas chromatography and mass spectrometry (Py-GC/MS) at 500°C. Monometallic modified catalysts were synthesized by loading 0.5 wt%, 1 wt%, and 2 wt% of metal species onto HZSM-5 using ion exchange methods. The composition and pyrolysis pathways of primary volatiles detectable by gas chromatography (GC) were investigated, which included phenols, aliphatic hydrocarbons, AHs, acids, furans, N-heterocyclic compounds (N-HCs), amides and nitriles. The relative yields in AHs increased about 10.9 (0.5 wt% Ni/HZSM-5 or Ni0.5), 10.2 (Ni1), 6.8 (Ni2), 7.3 (Co0.5), 9.7 (Co1) and 7.8 (Co2) times compared to the relative yield from defatted microalgae pyrolysis. The doping of metals onto the HZSM-5 altered its porosity and acidity, leading to an impaired diffusion of reactants but also the creation of new acidic sites, which enhanced the selectivity towards monoaromatic hydrocarbons (MAHs) by aromatization and cleavage of N-containing heterocycles via the H radicals formation. Ni-loaded HZSM-5 outperformed Co-modified zeolite with respect to AHs production, deoxygenation and denitrogenation. The specific surface area (SBET) and pore volume were positively correlated with the formation of AHs, while strong acidity showed a strong positive correlation with the generation of nitriles and N-HCs. Relatively low loadings of Ni and Co (0.5–1 wt%) on HZSM-5 (Si/Al = 23) were recommended to decrease the N-containing compounds in pyrolysis vapors from defatted microalgae. The findings may shed light on the development of a high-performance HZSM-5 catalyst for the production of AHs and denitrogenation from protein-rich defatted microalgae.
{"title":"Effects of porosity and acidity on deoxygenation and denitrogenation in catalytic pyrolysis of protein-rich microalgae with metal-doped zeolites","authors":"Qi Niu , Xin Du , Kai Li , Qiang Lu , Wolter Prins , Frederik Ronsse","doi":"10.1016/j.jaap.2024.106780","DOIUrl":"10.1016/j.jaap.2024.106780","url":null,"abstract":"<div><div>The protein-rich defatted microalgae (<em>Nannochloropsis gaditana</em>) after lipid extraction was used as feedstock in catalytic pyrolysis to optimize economic returns of microalgae waste utilization. The effects of Ni- and Co-modified HZSM-5 on the formation of aromatic hydrocarbons (AHs), deoxygenation and denitrogenation in catalytic fast pyrolysis were studied via pyrolysis-gas chromatography and mass spectrometry (Py-GC/MS) at 500°C. Monometallic modified catalysts were synthesized by loading 0.5 wt%, 1 wt%, and 2 wt% of metal species onto HZSM-5 using ion exchange methods. The composition and pyrolysis pathways of primary volatiles detectable by gas chromatography (GC) were investigated, which included phenols, aliphatic hydrocarbons, AHs, acids, furans, N-heterocyclic compounds (N-HCs), amides and nitriles. The relative yields in AHs increased about 10.9 (0.5 wt% Ni/HZSM-5 or Ni0.5), 10.2 (Ni1), 6.8 (Ni2), 7.3 (Co0.5), 9.7 (Co1) and 7.8 (Co2) times compared to the relative yield from defatted microalgae pyrolysis. The doping of metals onto the HZSM-5 altered its porosity and acidity, leading to an impaired diffusion of reactants but also the creation of new acidic sites, which enhanced the selectivity towards monoaromatic hydrocarbons (MAHs) by aromatization and cleavage of N-containing heterocycles via the H radicals formation. Ni-loaded HZSM-5 outperformed Co-modified zeolite with respect to AHs production, deoxygenation and denitrogenation. The specific surface area (S<sub>BET</sub>) and pore volume were positively correlated with the formation of AHs, while strong acidity showed a strong positive correlation with the generation of nitriles and N-HCs. Relatively low loadings of Ni and Co (0.5–1 wt%) on HZSM-5 (Si/Al = 23) were recommended to decrease the N-containing compounds in pyrolysis vapors from defatted microalgae. The findings may shed light on the development of a high-performance HZSM-5 catalyst for the production of AHs and denitrogenation from protein-rich defatted microalgae.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106780"},"PeriodicalIF":5.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142322572","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 : 2024-09-23DOI: 10.1016/j.jaap.2024.106779
Muthanna J. Ahmed , Bassim H. Hameed , Moonis Ali Khan
Cigarette butts/filters are recognized as one of the most dangerous wastes and environmental hazards worldwide due to their large quantities, non-biodegradability, and toxicity. Such wastes mainly consist of the plastic material cellulose acetate with a carbon-enriched structure, which can be a promising precursor for carbonaceous materials-based adsorbents. This review article discusses the production/modification, characterization, and utilization of carbonaceous materials-based adsorbents derived from cigarette butts/filters for aquatic pollutants removal. The most common forms of carbonaceous materials such as char, hydrochar, and activated carbon are considered. The influences of preparation/modification variables on the removal performance of such adsorbents are displayed. Moreover, the adsorption behavior under different conditions (i.e., solution pH, inlet contaminant amount, adsorbent quantity, and temperature) along with the mechanism and adsorbent reusability are also explained. The maximum uptakes of the most tested pollutants in terms of methylene blue, lead, ciprofloxacin, bisphenol A, and phenol were 635.2, 249.3, 556.2, 847.0, and 285.1 mg/g, respectively. The pseudo-second order kinetics equation and Langmuir isotherm best represented the adsorption data. Finally, the concluded notes and future suggestions are mentioned for the tested adsorbent/adsorbate systems.
{"title":"Recent progress on carbonaceous materials-based adsorbents derived from cigarette wastes for sustainable remediation of aquatic pollutants: A review","authors":"Muthanna J. Ahmed , Bassim H. Hameed , Moonis Ali Khan","doi":"10.1016/j.jaap.2024.106779","DOIUrl":"10.1016/j.jaap.2024.106779","url":null,"abstract":"<div><div>Cigarette butts/filters are recognized as one of the most dangerous wastes and environmental hazards worldwide due to their large quantities, non-biodegradability, and toxicity. Such wastes mainly consist of the plastic material cellulose acetate with a carbon-enriched structure, which can be a promising precursor for carbonaceous materials-based adsorbents. This review article discusses the production/modification, characterization, and utilization of carbonaceous materials-based adsorbents derived from cigarette butts/filters for aquatic pollutants removal. The most common forms of carbonaceous materials such as char, hydrochar, and activated carbon are considered. The influences of preparation/modification variables on the removal performance of such adsorbents are displayed. Moreover, the adsorption behavior under different conditions (i.e., solution pH, inlet contaminant amount, adsorbent quantity, and temperature) along with the mechanism and adsorbent reusability are also explained. The maximum uptakes of the most tested pollutants in terms of methylene blue, lead, ciprofloxacin, bisphenol A, and phenol were 635.2, 249.3, 556.2, 847.0, and 285.1 mg/g, respectively. The pseudo-second order kinetics equation and Langmuir isotherm best represented the adsorption data. Finally, the concluded notes and future suggestions are mentioned for the tested adsorbent/adsorbate systems.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106779"},"PeriodicalIF":5.8,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142314528","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 : 2024-09-22DOI: 10.1016/j.jaap.2024.106775
Menglong Niu , Yuhang Fang , Ben Niu , Liuyi Pan , Long Yu , Dong Li , Baoqi Ma
Kitchen waste oil (KWO) and coal tar (CT) are two commonly used alternatives to crude oil for fuel production through hydrogenation. If these two raw materials can be co-hydrogenated, it will help broaden the company's sources of raw materials. Therefore, in order to reveal the positive and negative impacts of the co-hydrogenation process of these two materials and to conduct a quantitative analysis of these phenomena, co-hydrogenation experiments of CT and KWO were completed in this study. The reaction kinetics parameters of the co-hydrogenation reaction were calculated. Experiments have shown that co-hydrogenation with coal tar hydrogenation products (CTHP) can increase the hydrogenation efficiency of KWO by approximately 1.5 %. This promoting effect is mainly attributed to the hydrogen-supplying properties of compounds such as tetralin and hexahydro naphthalene present in the CTHP. Through a combined model of reaction kinetics and thermodynamics, it is calculated that the activation energy of KWO hydrodeoxygenation under the action of catalysts is 50.936 kJ·mol−1, while under the action of CTHP hydrogen supply, it is 148.429 kJ·mol−1, and this promoting effect accounts for 19.3 % of the total reaction (as deduced from comparing reaction rate constants). The experimental data presented in this paper and the calculated reaction parameters can provide a basis for design improvements in technology.
{"title":"Analysis of the co-hydrogenation process of coal tar and kitchen waste oil based on reaction kinetics model","authors":"Menglong Niu , Yuhang Fang , Ben Niu , Liuyi Pan , Long Yu , Dong Li , Baoqi Ma","doi":"10.1016/j.jaap.2024.106775","DOIUrl":"10.1016/j.jaap.2024.106775","url":null,"abstract":"<div><div>Kitchen waste oil (KWO) and coal tar (CT) are two commonly used alternatives to crude oil for fuel production through hydrogenation. If these two raw materials can be co-hydrogenated, it will help broaden the company's sources of raw materials. Therefore, in order to reveal the positive and negative impacts of the co-hydrogenation process of these two materials and to conduct a quantitative analysis of these phenomena, co-hydrogenation experiments of CT and KWO were completed in this study. The reaction kinetics parameters of the co-hydrogenation reaction were calculated. Experiments have shown that co-hydrogenation with coal tar hydrogenation products (CTHP) can increase the hydrogenation efficiency of KWO by approximately 1.5 %. This promoting effect is mainly attributed to the hydrogen-supplying properties of compounds such as tetralin and hexahydro naphthalene present in the CTHP. Through a combined model of reaction kinetics and thermodynamics, it is calculated that the activation energy of KWO hydrodeoxygenation under the action of catalysts is 50.936 kJ·mol<sup>−1</sup>, while under the action of CTHP hydrogen supply, it is 148.429 kJ·mol<sup>−1</sup>, and this promoting effect accounts for 19.3 % of the total reaction (as deduced from comparing reaction rate constants). The experimental data presented in this paper and the calculated reaction parameters can provide a basis for design improvements in technology.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106775"},"PeriodicalIF":5.8,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142312998","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 : 2024-09-21DOI: 10.1016/j.jaap.2024.106758
Huijeong Kim , Woo-Bin Lee , Byeongcheol Lee , JeongHyun Kwon , Jae-Yong Ryu , Eilhann E. Kwon , Young-Min Kim
This study was conducted to establish the optimal pyrolysis process for producing high-yield and high-purity acetic acid (AA) from waste cigarette butts (CBs). The waste cigarette filters (CFs) were collected from CBs by shredding and sieving before pyrolysis. The non-isothermal pyrolysis of waste CF was studied using evolved gas analysis-mass spectrometry (EGA-MS) and double-shot pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) with tandem μ-reactor-GC/MS (TMR-GC/MS). EGA-MS of waste CF could differentiate the thermal desorption zones of tobacco additives, such as triacetin and glycerol tricaprylate, from the AA generation zone via cellulose acetate (CA) pyrolysis. The non-isothermal pyrolysis of CA, fresh CF, and waste CF from 100 °C to 400 °C at 20 °C/min resulted in AA as the primary product, with yields of 39.2 %, 34.8 %, and 36.2 %, respectively, along with the formation of additives, such as triacetin (8.8 wt% from waste CF) and glycerol tricaprylate as the main impurity. Despite the potential catalytic conversion of triacetin to AA using a mesoporous catalyst, Al-MCM-41 (SiO2/Al2O3: 25), the catalytic pyrolysis of waste CF did not enhance the high AA yield because of the additional conversion of AA, produced from CA in waste CF, into light hydrocarbons, reducing the AA yield. Finally, the optimized conditions for the highest quantity and quality AA production, achieving a total yield of 40.0 %, were determined to be a two-step selective catalytic conversion: 1) catalytic thermal desorption up to 300 °C using Al-MCM-41 at 350 °C and 2) non-catalytic pyrolysis for CA conversion from 301 °C to 400 °C of waste CF.
本研究旨在确定从废弃烟蒂（CBs）中生产高产高纯度醋酸（AA）的最佳热解工艺。在热解之前，通过粉碎和筛分从废烟蒂中收集了废香烟过滤嘴（CF）。利用气体分析-质谱法（EGA-MS）和双枪热解-气相色谱/质谱法（Py-GC/MS）与串联μ-反应器-气相色谱/质谱法（TMR-GC/MS）对废CF的非等温热解进行了研究。废 CF 的 EGA-MS 可将烟草添加剂（如三醋精和三辛酸甘油酯）的热解吸区与醋酸纤维素（CA）热解生成 AA 的区域区分开来。在 100 °C 至 400 °C 的温度范围内，以 20 °C/min 的速度对醋酸纤维素、新鲜 CF 和废 CF 进行非等温热解，其主要产物为 AA，产率分别为 39.2%、34.8% 和 36.2%，同时还生成了添加剂，如三醋精（废 CF 中占 8.8 wt%）和主要杂质三辛酸甘油酯。尽管使用介孔催化剂 Al-MCM-41（SiO2/Al2O3：25）可将三醋精催化转化为 AA，但催化热解废弃 CF 并不能提高 AA 的高产率，因为废弃 CF 中的 CA 产生的 AA 会额外转化为轻烃，从而降低 AA 的产率。最后，确定了生产最高数量和质量 AA（总产率达 40.0%）的优化条件，即两步选择性催化转化：1）在 350 ℃ 下使用 Al-MCM-41 进行高达 300 ℃ 的催化热解吸附；2）在 301 ℃ 至 400 ℃ 对废弃 CF 进行 CA 转化的非催化热解。
{"title":"Acetic acid production via the catalytic conversion of triacetin over Al-MCM-41 and the pyrolysis of cellulose acetate in waste cigarette filters","authors":"Huijeong Kim , Woo-Bin Lee , Byeongcheol Lee , JeongHyun Kwon , Jae-Yong Ryu , Eilhann E. Kwon , Young-Min Kim","doi":"10.1016/j.jaap.2024.106758","DOIUrl":"10.1016/j.jaap.2024.106758","url":null,"abstract":"<div><div>This study was conducted to establish the optimal pyrolysis process for producing high-yield and high-purity acetic acid (AA) from waste cigarette butts (CBs). The waste cigarette filters (CFs) were collected from CBs by shredding and sieving before pyrolysis. The non-isothermal pyrolysis of waste CF was studied using evolved gas analysis-mass spectrometry (EGA-MS) and double-shot pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) with tandem μ-reactor-GC/MS (TMR-GC/MS). EGA-MS of waste CF could differentiate the thermal desorption zones of tobacco additives, such as triacetin and glycerol tricaprylate, from the AA generation zone via cellulose acetate (CA) pyrolysis. The non-isothermal pyrolysis of CA, fresh CF, and waste CF from 100 °C to 400 °C at 20 °C/min resulted in AA as the primary product, with yields of 39.2 %, 34.8 %, and 36.2 %, respectively, along with the formation of additives, such as triacetin (8.8 wt% from waste CF) and glycerol tricaprylate as the main impurity. Despite the potential catalytic conversion of triacetin to AA using a mesoporous catalyst, Al-MCM-41 (SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub>: 25), the catalytic pyrolysis of waste CF did not enhance the high AA yield because of the additional conversion of AA, produced from CA in waste CF, into light hydrocarbons, reducing the AA yield. Finally, the optimized conditions for the highest quantity and quality AA production, achieving a total yield of 40.0 %, were determined to be a two-step selective catalytic conversion: 1) catalytic thermal desorption up to 300 °C using Al-MCM-41 at 350 °C and 2) non-catalytic pyrolysis for CA conversion from 301 °C to 400 °C of waste CF.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106758"},"PeriodicalIF":5.8,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142322570","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 : 2024-09-19DOI: 10.1016/j.jaap.2024.106770
Erfeng Hu , Yue Zhang , Zuohua Liu , Jianglong Yu , Qingang Xiong , Moshan Li , Yongfu Zeng
Co-pyrolysis has been studied for its potential to recycle energy from biomass and waste tyres, as well as enhance the quality of the bio-oil. In this paper, the TG-FTIR-GC/MS technique and a fast-infrared heated reactor were used to investigate the co-pyrolysis behaviors and mechanism of waste tyres (WT) and corn stover (CS). Based on the TG-FTIR-GC/MS analysis, co-pyrolysis synergy promoted the production of methane and aromatics while inhibiting the formation of CO2. Co-pyrolysis products distribution shows that the best synergy occurred at a ratio of 30 % WT with the highest oil yield deviation of 19.67 % and the lowest water yield deviation of −13.30 %. Response surface method (RSM) was utilized to optimize the oil production and the highest oil yield of 30.25 wt% was acquired at a heating rate of 25 °C/s and a ratio of 40 % WT. According to the oil analysis, the light fraction of oil (gasoline and diesel) was more than 50 % in all conditions and there was a large number of aromatics (more than 30 %) presented in oil. The char characteristics indicated that several metals combined with -S radicals during co-pyrolysis which formed much metal sulfide and sulfate in chars.
{"title":"Enhanced synergies for product distributions and interactions during co-pyrolysis between corn stover and tyres","authors":"Erfeng Hu , Yue Zhang , Zuohua Liu , Jianglong Yu , Qingang Xiong , Moshan Li , Yongfu Zeng","doi":"10.1016/j.jaap.2024.106770","DOIUrl":"10.1016/j.jaap.2024.106770","url":null,"abstract":"<div><div>Co-pyrolysis has been studied for its potential to recycle energy from biomass and waste tyres, as well as enhance the quality of the bio-oil. In this paper, the TG-FTIR-GC/MS technique and a fast-infrared heated reactor were used to investigate the co-pyrolysis behaviors and mechanism of waste tyres (WT) and corn stover (CS). Based on the TG-FTIR-GC/MS analysis, co-pyrolysis synergy promoted the production of methane and aromatics while inhibiting the formation of CO<sub>2</sub>. Co-pyrolysis products distribution shows that the best synergy occurred at a ratio of 30 % WT with the highest oil yield deviation of 19.67 % and the lowest water yield deviation of −13.30 %. Response surface method (RSM) was utilized to optimize the oil production and the highest oil yield of 30.25 wt% was acquired at a heating rate of 25 °C/s and a ratio of 40 % WT. According to the oil analysis, the light fraction of oil (gasoline and diesel) was more than 50 % in all conditions and there was a large number of aromatics (more than 30 %) presented in oil. The char characteristics indicated that several metals combined with -S radicals during co-pyrolysis which formed much metal sulfide and sulfate in chars.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106770"},"PeriodicalIF":5.8,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142314522","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 : 2024-09-19DOI: 10.1016/j.jaap.2024.106771
Liying Tian , Shengyong Liu , Nadeem Tahir , Li Huang , Hongge Tao , Dengke Zhao , Jiawei Wang , Junmeng Cai
Distillers dried grains with solubles (DDGS) offer high calorific value, suited for catalytic rapid pyrolysis for energy and chemical applications, yet tar and coke formation during bio-oil upgrading necessitates exploration of cost-effective, durable biocarbon-based catalysts for tar removal. In this study, a carbon-based catalyst was prepared by metal modification of alkaline biochar for catalytic pyrolysis with Distillers dried grains with solubles (DDGS) biomass. Brunauer–Emmet–Teller (BET), X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) were used to characterized the morphology and microstructure of the metal-modified carbon-based catalysts. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was used to analysis the pyrolysis-gas of catalytic pyrolysis. Furthermore, the effects of the loading and metal mass ratio of carbon-based monometallic catalysts (Fe and Co) and carbon-based bimetallic catalysts (Fe-Co) on the distribution of the DDGS pyrolysis products were further investigated. The results showed that the 8 wt% of loading rate of bimetallic catalyst significantly reduced the oxygenated compounds but increased the aromatic hydrocarbons. Compared with pyrolysis without catalyst, when the catalyst was 2Fe6Co (mass ratio of Fe/Co 1:3), the hydrocarbons increased from 36.42 % to 44.53 %, the oxygen-containing compounds decreased from 60.36 % to 52.35 %, and the aromatics increased significantly from 0.73 % to 25.37 %. This study provides a new route of increasing the aromatic hydrocarbon content of catalytic pyrolysis to offer theoretical basis for carbon-based catalysts of biomass conversion.
{"title":"Preparation of metal-modified carbon-based catalyst and experimental study on catalytic pyrolysis of distillers dried grains with solubles","authors":"Liying Tian , Shengyong Liu , Nadeem Tahir , Li Huang , Hongge Tao , Dengke Zhao , Jiawei Wang , Junmeng Cai","doi":"10.1016/j.jaap.2024.106771","DOIUrl":"10.1016/j.jaap.2024.106771","url":null,"abstract":"<div><div>Distillers dried grains with solubles (DDGS) offer high calorific value, suited for catalytic rapid pyrolysis for energy and chemical applications, yet tar and coke formation during bio-oil upgrading necessitates exploration of cost-effective, durable biocarbon-based catalysts for tar removal. In this study, a carbon-based catalyst was prepared by metal modification of alkaline biochar for catalytic pyrolysis with Distillers dried grains with solubles (DDGS) biomass. Brunauer–Emmet–Teller (BET), X-ray diffraction (XRD), Fourier Transform Infrared (FTIR) were used to characterized the morphology and microstructure of the metal-modified carbon-based catalysts. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was used to analysis the pyrolysis-gas of catalytic pyrolysis. Furthermore, the effects of the loading and metal mass ratio of carbon-based monometallic catalysts (Fe and Co) and carbon-based bimetallic catalysts (Fe-Co) on the distribution of the DDGS pyrolysis products were further investigated. The results showed that the 8 wt% of loading rate of bimetallic catalyst significantly reduced the oxygenated compounds but increased the aromatic hydrocarbons. Compared with pyrolysis without catalyst, when the catalyst was 2Fe6Co (mass ratio of Fe/Co 1:3), the hydrocarbons increased from 36.42 % to 44.53 %, the oxygen-containing compounds decreased from 60.36 % to 52.35 %, and the aromatics increased significantly from 0.73 % to 25.37 %. This study provides a new route of increasing the aromatic hydrocarbon content of catalytic pyrolysis to offer theoretical basis for carbon-based catalysts of biomass conversion.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106771"},"PeriodicalIF":5.8,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313000","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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