Pub Date : 2024-12-30DOI: 10.1016/j.jaap.2024.106934
Xin Hou , Penggang Ren , Wenhui Tian , BaoLi Fan , Tong Wu , Jiayi Wang , Zhiyuan Duan , Zhengyan Chen , Yanling Jin
Although hierarchical porous carbon materials are widely used in supercapacitors, the poor accessibility and long diffusion distance for ion caused by collapsible carbon hinder the practical application. Constructing structurally stable precursors and fully using internal space is crucial for the preparation of hierarchical porous carbon and the enhancement of its capacitive properties. Herein, a porous carbon with a robust cross-linked network is prepared from gelatin via an ice crystal-assisted chemical activation strategy. The formed cavities regulated by volume in ice crystals template ensure the integrity of carbon framework and highly accessible surface area for activators. This unique structure endows the as-prepared hierarchical porous carbon with a high surface area (2684.5 m2/g). Furthermore, accompanied by the inheritance heteroatoms (N and O) from gelatin, the resultant carbon displays a desirable specific capacitance of 453.7 F/g at 1 A/g and retain 74.4 % capacitance at 20 A/g in the three-electrode system. This work provides insights into regulating the pore structure of biomass-based carbon aerogels, which is essential for developing bio-based, environmentally friendly and sustainable energy storage materials.
{"title":"Preparation of biomass-derived porous carbon aerogels via ice template-assisted chemical activation for high-performance supercapacitors","authors":"Xin Hou , Penggang Ren , Wenhui Tian , BaoLi Fan , Tong Wu , Jiayi Wang , Zhiyuan Duan , Zhengyan Chen , Yanling Jin","doi":"10.1016/j.jaap.2024.106934","DOIUrl":"10.1016/j.jaap.2024.106934","url":null,"abstract":"<div><div>Although hierarchical porous carbon materials are widely used in supercapacitors, the poor accessibility and long diffusion distance for ion caused by collapsible carbon hinder the practical application. Constructing structurally stable precursors and fully using internal space is crucial for the preparation of hierarchical porous carbon and the enhancement of its capacitive properties. Herein, a porous carbon with a robust cross-linked network is prepared from gelatin via an ice crystal-assisted chemical activation strategy. The formed cavities regulated by volume in ice crystals template ensure the integrity of carbon framework and highly accessible surface area for activators. This unique structure endows the as-prepared hierarchical porous carbon with a high surface area (2684.5 m<sup>2</sup>/g). Furthermore, accompanied by the inheritance heteroatoms (N and O) from gelatin, the resultant carbon displays a desirable specific capacitance of 453.7 F/g at 1 A/g and retain 74.4 % capacitance at 20 A/g in the three-electrode system. This work provides insights into regulating the pore structure of biomass-based carbon aerogels, which is essential for developing bio-based, environmentally friendly and sustainable energy storage materials.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106934"},"PeriodicalIF":5.8,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143171940","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 : 2024-12-30DOI: 10.1016/j.jaap.2024.106941
Kai Li , Wan-zhao Huang , Dong-hong Nan , Qi Niu , Xi Luo , Bin Hu , Dan Yan , Qiang Lu
A new method for the sustainable utilization of waste lithium-ion battery separators was developed, involving the hydrochloric acid washing to partially remove the Al2O3 coating, followed by catalytic pyrolysis to produce aromatic hydrocarbons with HZSM-5. The separators composed of polyethylene as base film were selected as the feedstock. The effects of acid washing pretreatment on the physicochemical properties and pyrolysis characteristics of the separators were studied. The results showed that the partial removal of Al2O3 coating not only enhanced the heat and mass transfer, improving the primary thermal decomposition of organic matter and increasing the formation of volatiles, but also promoted the contact between volatiles and Al2O3, resulting in the cracking of large molecular substances into small molecular olefins. This pretreatment process was conducive to the production of aromatic hydrocarbons during the catalytic pyrolysis over HZSM-5. The aromatic hydrocarbons yield, calculated based on the ash-free separator, reached a maximum value of 83.20 wt% under conditions of 1.5 mol/L hydrochloric acid concentration and a catalyst/separator ratio of 12 at 650℃. This yield surpassed the yields of 59.24 wt% from untreated separator and 64.39 wt% from pure polyethylene separator.
{"title":"Partial removal of Al2O3 enhanced production of aromatic hydrocarbons from catalytic pyrolysis of waste lithium-ion battery separators","authors":"Kai Li , Wan-zhao Huang , Dong-hong Nan , Qi Niu , Xi Luo , Bin Hu , Dan Yan , Qiang Lu","doi":"10.1016/j.jaap.2024.106941","DOIUrl":"10.1016/j.jaap.2024.106941","url":null,"abstract":"<div><div>A new method for the sustainable utilization of waste lithium-ion battery separators was developed, involving the hydrochloric acid washing to partially remove the Al<sub>2</sub>O<sub>3</sub> coating, followed by catalytic pyrolysis to produce aromatic hydrocarbons with HZSM-5. The separators composed of polyethylene as base film were selected as the feedstock. The effects of acid washing pretreatment on the physicochemical properties and pyrolysis characteristics of the separators were studied. The results showed that the partial removal of Al<sub>2</sub>O<sub>3</sub> coating not only enhanced the heat and mass transfer, improving the primary thermal decomposition of organic matter and increasing the formation of volatiles, but also promoted the contact between volatiles and Al<sub>2</sub>O<sub>3</sub>, resulting in the cracking of large molecular substances into small molecular olefins. This pretreatment process was conducive to the production of aromatic hydrocarbons during the catalytic pyrolysis over HZSM-5. The aromatic hydrocarbons yield, calculated based on the ash-free separator, reached a maximum value of 83.20 wt% under conditions of 1.5 mol/L hydrochloric acid concentration and a catalyst/separator ratio of 12 at 650℃. This yield surpassed the yields of 59.24 wt% from untreated separator and 64.39 wt% from pure polyethylene separator.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106941"},"PeriodicalIF":5.8,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143171931","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 : 2024-12-28DOI: 10.1016/j.jaap.2024.106943
Zhi-Min Wang , Du Wang , Ling-Nan Wu , Cheng-Yin Ye , Zi-Qiang Zhu , Zhen-Yu Tian
N-methylpyrrolidone (NMP) is essential in lithium-ion battery production. Its thermal decomposition raises concerns regarding the environment, human health, and sustainable battery manufacturing practices. In this work, M062X/6–311 + +G(d,p) and CCSD(T)-F12a/cc-pVTZ-F12 calculations methods were employed to explore the crucial H-abstraction reactions, bond dissociation energies, and potential energy surfaces of NMP pyrolysis. A pyrolysis kinetic model was developed, encompassing 969 species and 5391 reactions, to provide insights into the NMP pyrolysis process. The results reveal that the H-abstraction reactions significantly contribute to NMP decomposition, particularly at lower temperature region within 900–1200 K. The carbon site adjacent to nitrogen atoms on the five-membered ring is found to be more energetically favorable, and the branching ratio of this channel decreases gradually with temperature increasing. As the temperature increases, the effect of the C8 site attenuates gradually, yielding to the C2-H and C11-CH3 sites which emerge as the predominant channels for decomposition, facilitated by H-abstraction reactions by H and CH3 radicals. Rate coefficients of these reactions were determined through RRKM/ME calculations, and the model was validated against available experimental data. Rate-of-production analysis indicates that H-abstraction reactions dominate NMP consumption (over 98 %) at 1050 K, playing more important roles than unimolecular decompositions. Sensitivity analysis at 1050 K identifies that CH2NCH2+HCH3NCH2 and NMP=NMP-11 +H have the most obvious inhibiting and promoting effects on NMP consumption, respectively. A promising but under-research study was also identified in present work, along with discussions on their implications for future investigation. By understanding the behavior of NMP during pyrolysis, the battery manufacturing process could be optimized to reduce its environmental impact.
{"title":"Theoretical and kinetic modeling investigation of N-methylpyrrolidone","authors":"Zhi-Min Wang , Du Wang , Ling-Nan Wu , Cheng-Yin Ye , Zi-Qiang Zhu , Zhen-Yu Tian","doi":"10.1016/j.jaap.2024.106943","DOIUrl":"10.1016/j.jaap.2024.106943","url":null,"abstract":"<div><div>N-methylpyrrolidone (NMP) is essential in lithium-ion battery production. Its thermal decomposition raises concerns regarding the environment, human health, and sustainable battery manufacturing practices. In this work, M062X/6–311 + +G(d,p) and CCSD(T)-F12a/cc-pVTZ-F12 calculations methods were employed to explore the crucial H-abstraction reactions, bond dissociation energies, and potential energy surfaces of NMP pyrolysis. A pyrolysis kinetic model was developed, encompassing 969 species and 5391 reactions, to provide insights into the NMP pyrolysis process. The results reveal that the H-abstraction reactions significantly contribute to NMP decomposition, particularly at lower temperature region within 900–1200 K. The carbon site adjacent to nitrogen atoms on the five-membered ring is found to be more energetically favorable, and the branching ratio of this channel decreases gradually with temperature increasing. As the temperature increases, the effect of the C8 site attenuates gradually, yielding to the C2-H and C11-CH<sub>3</sub> sites which emerge as the predominant channels for decomposition, facilitated by H-abstraction reactions by H and CH<sub>3</sub> radicals. Rate coefficients of these reactions were determined through RRKM/ME calculations, and the model was validated against available experimental data. Rate-of-production analysis indicates that H-abstraction reactions dominate NMP consumption (over 98 %) at 1050 K, playing more important roles than unimolecular decompositions. Sensitivity analysis at 1050 K identifies that CH<sub>2</sub>NCH<sub>2</sub>+H<img>CH<sub>3</sub>NCH<sub>2</sub> and NMP=NMP-11 +H have the most obvious inhibiting and promoting effects on NMP consumption, respectively. A promising but under-research study was also identified in present work, along with discussions on their implications for future investigation. By understanding the behavior of NMP during pyrolysis, the battery manufacturing process could be optimized to reduce its environmental impact.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106943"},"PeriodicalIF":5.8,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172823","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 : 2024-12-27DOI: 10.1016/j.jaap.2024.106940
Ting Li , Ting He , Jiang Wei , Lilong Zhang , Xiaohua Lu , Hongliang Qian
The type and proportion of biomass pyrolysis products are determined by both biomass composition and operating conditions. Although the effect of operating conditions has been extensively investigated, the influence of biomass composition, especially the degree of polymerization, has seldom been explored. In this work, cellulose samples with different degrees of polymerization were prepared by soda-oxygen cooking, and the viscosity of the cellulose was determined to obtain the degree of polymerization. Then, an accurate prediction model of the higher heating value of cellulose was successfully established by incorporating the degree of polymerization, and the relative error range was reduced from 13 %-17 % to 0.25 %-1.0 %. Finally, the effect of the degree of polymerization on the gas products of cellulose pyrolysis (H2, CO, CH4, CO2) was explored through process simulation with the help of Gibbs free energy minimization. The results showed that as the increase of the degree of polymerization, the amount of H2 increased and the amount of CO decreased. This work serves as a preliminary investigation of the effect of the degree of polymerization on cellulose pyrolysis in theory based on thermochemical data. It can be used as a valuable reference for the further study of the effect of degree of polymerization on polymer pyrolysis.
{"title":"Study on the effect of degree of polymerization of cellulose on syngas composition based on established higher heating value prediction model","authors":"Ting Li , Ting He , Jiang Wei , Lilong Zhang , Xiaohua Lu , Hongliang Qian","doi":"10.1016/j.jaap.2024.106940","DOIUrl":"10.1016/j.jaap.2024.106940","url":null,"abstract":"<div><div>The type and proportion of biomass pyrolysis products are determined by both biomass composition and operating conditions. Although the effect of operating conditions has been extensively investigated, the influence of biomass composition, especially the degree of polymerization, has seldom been explored. In this work, cellulose samples with different degrees of polymerization were prepared by soda-oxygen cooking, and the viscosity of the cellulose was determined to obtain the degree of polymerization. Then, an accurate prediction model of the higher heating value of cellulose was successfully established by incorporating the degree of polymerization, and the relative error range was reduced from 13 %-17 % to 0.25 %-1.0 %. Finally, the effect of the degree of polymerization on the gas products of cellulose pyrolysis (H<sub>2</sub>, CO, CH<sub>4</sub>, CO<sub>2</sub>) was explored through process simulation with the help of Gibbs free energy minimization. The results showed that as the increase of the degree of polymerization, the amount of H<sub>2</sub> increased and the amount of CO decreased. This work serves as a preliminary investigation of the effect of the degree of polymerization on cellulose pyrolysis in theory based on thermochemical data. It can be used as a valuable reference for the further study of the effect of degree of polymerization on polymer pyrolysis.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106940"},"PeriodicalIF":5.8,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143171938","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 : 2024-12-26DOI: 10.1016/j.jaap.2024.106939
Ming Zhang , Siyuan Huang , Zhongyuan Wang , Guodong Wang , Qi Jiang , Kuncheng Li , Dian Fan
In-situ solvent generation enhanced steam assisted gravity drainage (ISSG-SAGD) is proposed to enhance heavy oil recovery while reducing steam use and carbon emissions. The study experimentally investigated the generation, migration, and condensation of light hydrocarbons (LHs) during thermal cracking of heavy oil (TCHO). The key objective was to assess the feasibility of in-situ solvent generation as a replacement for external solvent injection in SAGD processes. Experiments were conducted under high-temperature and high-pressure conditions to facilitate LHs generation, followed by distillation to simulate solvent migration and condensation within the steam chamber. The composition of generated LHs was analyzed using gas chromatography-mass spectrometry (GC-MS). Under conditions of 360–400 ℃ and reaction times of 12–96 hours, target solvent yields varied from 3.29 to 35.04 wt%, primary consisting of C1-C13 components. Notably, at 360 ℃ for 12 hours, the solvent concentration reached approximately 0.25–0.99 wt%, which is comparable to successful solvent assisted SAGD projects that utilize solvent concentrations of ≥ 1 wt%. The results suggest that in-situ solvent generation can enhance SAGD efficiency similarly to external solvent injection, without the additional costs of solvent procurement and injection. This research highlights the potential of ISSG-SAGD to optimize steam use and improve economic efficiency while maintaining effective oil drainage, paving the way for more efficient heavy oil recovery.
{"title":"Experimental investigation of in-situ solvent generation for SAGD and Its effectiveness in heavy oil recovery","authors":"Ming Zhang , Siyuan Huang , Zhongyuan Wang , Guodong Wang , Qi Jiang , Kuncheng Li , Dian Fan","doi":"10.1016/j.jaap.2024.106939","DOIUrl":"10.1016/j.jaap.2024.106939","url":null,"abstract":"<div><div>In-situ solvent generation enhanced steam assisted gravity drainage (ISSG-SAGD) is proposed to enhance heavy oil recovery while reducing steam use and carbon emissions. The study experimentally investigated the generation, migration, and condensation of light hydrocarbons (LHs) during thermal cracking of heavy oil (TCHO). The key objective was to assess the feasibility of in-situ solvent generation as a replacement for external solvent injection in SAGD processes. Experiments were conducted under high-temperature and high-pressure conditions to facilitate LHs generation, followed by distillation to simulate solvent migration and condensation within the steam chamber. The composition of generated LHs was analyzed using gas chromatography-mass spectrometry (GC-MS). Under conditions of 360–400 ℃ and reaction times of 12–96 hours, target solvent yields varied from 3.29 to 35.04 wt%, primary consisting of C<sub>1</sub>-C<sub>13</sub> components. Notably, at 360 ℃ for 12 hours, the solvent concentration reached approximately 0.25–0.99 wt%, which is comparable to successful solvent assisted SAGD projects that utilize solvent concentrations of ≥ 1 wt%. The results suggest that in-situ solvent generation can enhance SAGD efficiency similarly to external solvent injection, without the additional costs of solvent procurement and injection. This research highlights the potential of ISSG-SAGD to optimize steam use and improve economic efficiency while maintaining effective oil drainage, paving the way for more efficient heavy oil recovery.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106939"},"PeriodicalIF":5.8,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173872","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 : 2024-12-26DOI: 10.1016/j.jaap.2024.106932
Argha Bhattacharjee , Shani Saha , Jay Patel , Arvind Kumar , Arindrajit Chowdhury , Neeraj Kumbhakarna
The emergence of azole-grafted hydroxyl-terminated polybutadiene (HTPB), specifically tetrazole-grafted HTPB (Tetz-HTPB), has sparked considerable interest recently owing to its remarkable energetic properties, synthetic capabilities, and physicochemical characteristics as an energetic binder (EB) for solid rocket propellant (SRP) compositions. The current study focusses on an extensive examination of the thermal properties of this new binder under slow pyrolysis condition using TGA-DTG and c-DTA analyses. To comprehend the complex bond-breaking mechanisms of polymer-based materials, the initial stage decomposition of Tetz-HTPB in the condensed phase was analysed by integrating experimental and theoretical methods. The experimental study clarifies that, unlike HTPB, the initial stage breakdown of Tetz-HTPB occurs at 190 °C with the release of N2 and HCN as primary gaseous products, while thermal crosslinking of this polymer does not commence at this stage and instead starts at 290 °C. Such peculiar experimental outcome, later supported by quantum mechanics computations, offers valuable insights into the mechanism of bond-breaking at this stage. Further kinetic analysis showed that Tetz-HTPB has somewhat shorter shelf life than HTPB and Nitro-HTPB due to its low reaction constant value, 4.4E-07 min−1 at 50 °C, even at closed pierced lid conditions. Moreover, the current research explores multiple aspects of the thermal properties of Tetz-HTPB, including the initial stage decomposition mechanism, shelf-life behaviour for long-term storage, etc. with an emphasis on its potential use as an EB in cutting-edge propellant research and development.
{"title":"Unveiling the early-stage condensed-phase decomposition of tetrazole-grafted HTPB as energetic binder-experimental and quantum mechanistic revelations","authors":"Argha Bhattacharjee , Shani Saha , Jay Patel , Arvind Kumar , Arindrajit Chowdhury , Neeraj Kumbhakarna","doi":"10.1016/j.jaap.2024.106932","DOIUrl":"10.1016/j.jaap.2024.106932","url":null,"abstract":"<div><div>The emergence of azole<em>-grafted</em> hydroxyl-terminated polybutadiene (HTPB), specifically tetrazole<em>-grafted</em> HTPB (Tetz-HTPB), has sparked considerable interest recently owing to its remarkable energetic properties, synthetic capabilities, and physicochemical characteristics as an energetic binder (EB) for solid rocket propellant (SRP) compositions. The current study focusses on an extensive examination of the thermal properties of this new binder under slow pyrolysis condition using TGA-DTG and c-DTA analyses. To comprehend the complex bond-breaking mechanisms of polymer-based materials, the initial stage decomposition of Tetz-HTPB in the condensed phase was analysed by integrating experimental and theoretical methods. The experimental study clarifies that, unlike HTPB, the initial stage breakdown of Tetz-HTPB occurs at 190 °C with the release of N<sub>2</sub> and HCN as primary gaseous products, while thermal crosslinking of this polymer does not commence at this stage and instead starts at 290 °C. Such peculiar experimental outcome, later supported by quantum mechanics computations, offers valuable insights into the mechanism of bond-breaking at this stage. Further kinetic analysis showed that Tetz-HTPB has somewhat shorter shelf life than HTPB and Nitro-HTPB due to its low reaction constant value, 4.4E-07 min<sup>−1</sup> at 50 °C, even at closed pierced lid conditions. Moreover, the current research explores multiple aspects of the thermal properties of Tetz-HTPB, including the initial stage decomposition mechanism, shelf-life behaviour for long-term storage, etc. with an emphasis on its potential use as an EB in cutting-edge propellant research and development.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106932"},"PeriodicalIF":5.8,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143171932","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 : 2024-12-25DOI: 10.1016/j.jaap.2024.106937
Mohammed Abobakr Al-Maari , Mohd Azmier Ahmad , Azam Taufik Mohd Din , Hamizura Hassan , Ahmed Mubarak Alsobaai
The cost-effective upgradation of pyrolysis oil is a significant challenge that hinders the commercial production of biomass biofuels. This research aimed to enhance bio-oil production by co-feeding low-density polyethylene (LDPE) with palm oil empty fruit bunch (EFB) waste using a natural clinoptilolite catalyst in a fixed-bed reactor. The impact of pyrolysis temperature and the catalyst-to-feedstock (C/F) ratio on the yields and chemical composition of the bio-oil were examined. Clinoptilolite significantly enhanced the yield of the bio-oil as well as its chemical composition. The maximum yield of bio-oil (72.6 %) with a yield of hydrocarbons (77.6 %) were attained at 500 °C, using a C/F mass ratio of 0.2. Liquid oil produced using clinoptilolite catalyst exhibited a high heating value (HHV) (44.2MJ/kg), which is comparable to conventional diesel.
{"title":"Upgrading bio-oil production via catalytic co-pyrolysis of oil palm empty fruit bunch and low-density polyethylene using clinoptilolite catalyst","authors":"Mohammed Abobakr Al-Maari , Mohd Azmier Ahmad , Azam Taufik Mohd Din , Hamizura Hassan , Ahmed Mubarak Alsobaai","doi":"10.1016/j.jaap.2024.106937","DOIUrl":"10.1016/j.jaap.2024.106937","url":null,"abstract":"<div><div>The cost-effective upgradation of pyrolysis oil is a significant challenge that hinders the commercial production of biomass biofuels. This research aimed to enhance bio-oil production by co-feeding low-density polyethylene (LDPE) with palm oil empty fruit bunch (EFB) waste using a natural clinoptilolite catalyst in a fixed-bed reactor. The impact of pyrolysis temperature and the catalyst-to-feedstock (C/F) ratio on the yields and chemical composition of the bio-oil were examined. Clinoptilolite significantly enhanced the yield of the bio-oil as well as its chemical composition. The maximum yield of bio-oil (72.6 %) with a yield of hydrocarbons (77.6 %) were attained at 500 °C, using a C/F mass ratio of 0.2. Liquid oil produced using clinoptilolite catalyst exhibited a high heating value (HHV) (44.2MJ/kg), which is comparable to conventional diesel.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106937"},"PeriodicalIF":5.8,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143171936","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 : 2024-12-25DOI: 10.1016/j.jaap.2024.106936
Shengtao Qi , Xiaorong Zhang , Shanjian Liu , Linghao Ran , Weiming Yi , Zhihe Li , Andong Zhang , Deli Zhang , Lihong Wang
The co-processing of bio-oil with petroleum feedstocks is an effective strategy for enhancing commercial utilization of bio-oil, potentially facilitating the large-scale production of biofuel or oxygenated chemicals. However, the co-processing efficiency is limited by the high acid and oxygen concentrations present in bio-oil. The performance of bio-oil can be enhanced by reducing acidity and facilitating the growth of ketones and carbon chain. In this study, the influence of the reduction properties of red mud (RM) on pyrolysis products of corn stover (CS) using online catalysis was investigated. The enriching mechanism of ketones and phenols in bio-oil was also elucidated. The results showed that Fe₂O₃ transformed to Fe₃O₄ in reduced RM (RRM), increasing oxygen vacancy in the surface and larger specific surface area, acid and base sites were observed in the RRM, which not only enhanced the ketonization reactions of acids, aldehydes, esters and sugars, but also the alkylation of phenols. RM reduced at 500°C is more effective than other reduction temperatures, significantly reducing carboxylic acid content from 20.49 % to 10.51 % before catalysis. Concurrently, phenol and ketone contents increased from 20.47 % and 16.61-30.51 % and 22.72 %, respectively. The production of ketones was enhanced within moderate reaction temperatures of 400-500°C, whereas the formation of phenols was optimal at higher temperatures (550°C). This study presents a novel approach to mild deoxygenation of biomass and the cost-effective production of ketone- and phenol-enriched bio-oil.
{"title":"Mild upgrading of biomass pyrolysis vapors via ex-situ catalytic pyrolysis using reduced red mud catalyst","authors":"Shengtao Qi , Xiaorong Zhang , Shanjian Liu , Linghao Ran , Weiming Yi , Zhihe Li , Andong Zhang , Deli Zhang , Lihong Wang","doi":"10.1016/j.jaap.2024.106936","DOIUrl":"10.1016/j.jaap.2024.106936","url":null,"abstract":"<div><div>The co-processing of bio-oil with petroleum feedstocks is an effective strategy for enhancing commercial utilization of bio-oil, potentially facilitating the large-scale production of biofuel or oxygenated chemicals. However, the co-processing efficiency is limited by the high acid and oxygen concentrations present in bio-oil. The performance of bio-oil can be enhanced by reducing acidity and facilitating the growth of ketones and carbon chain. In this study, the influence of the reduction properties of red mud (RM) on pyrolysis products of corn stover (CS) using online catalysis was investigated. The enriching mechanism of ketones and phenols in bio-oil was also elucidated. The results showed that Fe₂O₃ transformed to Fe₃O₄ in reduced RM (RRM), increasing oxygen vacancy in the surface and larger specific surface area, acid and base sites were observed in the RRM, which not only enhanced the ketonization reactions of acids, aldehydes, esters and sugars, but also the alkylation of phenols. RM reduced at 500°C is more effective than other reduction temperatures, significantly reducing carboxylic acid content from 20.49 % to 10.51 % before catalysis. Concurrently, phenol and ketone contents increased from 20.47 % and 16.61-30.51 % and 22.72 %, respectively. The production of ketones was enhanced within moderate reaction temperatures of 400-500°C, whereas the formation of phenols was optimal at higher temperatures (550°C). This study presents a novel approach to mild deoxygenation of biomass and the cost-effective production of ketone- and phenol-enriched bio-oil.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106936"},"PeriodicalIF":5.8,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143173871","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 : 2024-12-24DOI: 10.1016/j.jaap.2024.106933
Lei Jiang , Xiong Zhang , Jiang Liu , Junjie Zhang , Jingai Shao , Shihong Zhang , Haiping Yang , Hanping Chen
Utilizing renewable bio-pitch to replace coal tar pitch for carbon anode production is an attractive route away from fossil fuel dependence and environmental pollution. However, it is urgent but challenging for the quality to meet the standards of binder pitch. Herein, to improve the quinoline insoluble content and coking value, the distillation characteristics of two bio-oils as well as the effects of distillation temperature, time and additives on the physicochemical properties of bio-pitch were investigated. The results showed that when the temperature was increased from at 160 °C to 220 °C, the solid phase products of BO1 and BO2 bio-oil distillation decreased by 17.6 % and 14 %, respectively, and the toluene insoluble content, coking value, quinoline insoluble content, and the softening point of the bio-pitch gradually increased. Prolonged distillation time showed limited improvement in asphalt properties. The addition of appropriate amounts of styrene, isopropanol or biochar improved the coking value and quinoline insoluble content of bio-pitch. This work provided a reference for the preparation of bio-pitch that meets the criteria for binder use.
{"title":"Simple distillation to obtain bio-pitch from bio-oil for carbon anode production","authors":"Lei Jiang , Xiong Zhang , Jiang Liu , Junjie Zhang , Jingai Shao , Shihong Zhang , Haiping Yang , Hanping Chen","doi":"10.1016/j.jaap.2024.106933","DOIUrl":"10.1016/j.jaap.2024.106933","url":null,"abstract":"<div><div>Utilizing renewable bio-pitch to replace coal tar pitch for carbon anode production is an attractive route away from fossil fuel dependence and environmental pollution. However, it is urgent but challenging for the quality to meet the standards of binder pitch. Herein, to improve the quinoline insoluble content and coking value, the distillation characteristics of two bio-oils as well as the effects of distillation temperature, time and additives on the physicochemical properties of bio-pitch were investigated. The results showed that when the temperature was increased from at 160 °C to 220 °C, the solid phase products of BO1 and BO2 bio-oil distillation decreased by 17.6 % and 14 %, respectively, and the toluene insoluble content, coking value, quinoline insoluble content, and the softening point of the bio-pitch gradually increased. Prolonged distillation time showed limited improvement in asphalt properties. The addition of appropriate amounts of styrene, isopropanol or biochar improved the coking value and quinoline insoluble content of bio-pitch. This work provided a reference for the preparation of bio-pitch that meets the criteria for binder use.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106933"},"PeriodicalIF":5.8,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143171935","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 : 2024-12-24DOI: 10.1016/j.jaap.2024.106931
Lili Fu , Jingmei Han , Qi Zhang , Chuan Liu , Ke Zhang , Yue Zhang , Chunping Wang , Zilong Zhang , Xinyan Jin , Xiaofeng Wang , Le Wang , Ping Lei , Bin Li
<div><div>Electrically heated tobacco products (eHTPs) are novel products that could potentially reduce health risks relative to smoking. A series of thermal physico-chemical processes occur in tobacco materials while an eHTP is consumed under designed heating conditions. In order to establish a quantitative characterization of the thermal state of the tobacco materials in eHTPs, this study proposed a universal and systematic framework to evaluate the thermal state of eHTPs, irrespective of the heating technology used by the heating device (e.g., central vs. peripheral, radiation vs. induction, etc). For this purpose, a physical concept of thermal state <span><math><mover><mrow><mi>η</mi><mspace></mspace></mrow><mo>ˆ</mo></mover></math></span>of eHTPs was defined, which indicated the quantities and the compositions of the aerosol released, and a characteristic temperature <span><math><mover><mrow><mi>T</mi></mrow><mo>ˆ</mo></mover></math></span> was also introduced. The framework uses the Pearson correlation to conduct dimensionless treatment on the thermal conversion efficiency of the working eHTPs, which took into account the effective migration of key aerosol components, the release of harmful or potentially harmful constituents (HPHCs), and the oxygen consumption of the thermal processing involved. The framework then defined a combination of datasets corresponding to <span><math><mover><mrow><mi>η</mi></mrow><mo>ˆ</mo></mover></math></span>, which involved 8 key thermophysical indicators, such as the tobacco's thermal mass loss, the oxygen consumption rate and carbon monoxide formation, the release of nicotine, glycerol and total particulate matter, and the release of acetaldehyde and toluene as markers of volatile HPHCs. Under the assumption of a unique relation between <span><math><mover><mrow><mi>η</mi></mrow><mo>ˆ</mo></mover></math></span> and <span><math><mover><mrow><mi>T</mi></mrow><mo>ˆ</mo></mover></math></span>, the numerical function between volume average temperature<span><math><mrow><mspace></mspace><mover><mrow><mi>T</mi></mrow><mo>̅</mo></mover></mrow></math></span> and <span><math><mover><mrow><mi>T</mi></mrow><mo>ˆ</mo></mover></math></span> of the tobacco materials under different heating conditions was obtained by a modified factor method, and the function set <em>f</em>(<span><math><mover><mrow><mi>T</mi></mrow><mo>ˆ</mo></mover></math></span>) was established. When <span><math><mover><mrow><mi>T</mi></mrow><mo>ˆ</mo></mover></math></span> value of 240 ℃ was served as a key reference temperature, its corresponding <span><math><msub><mrow><mover><mrow><mi>η</mi></mrow><mo>ˆ</mo></mover></mrow><mrow><mi>W</mi></mrow></msub></math></span> (substance) was 0.46, the corresponding <span><math><mover><mrow><mi>η</mi></mrow><mo>ˆ</mo></mover></math></span> values for nicotine and glycerol are above 0.85, approaching full release for the two key aerosol substances, with a lower oxygen consumption and the release of HPHCs. Under th
{"title":"Thermal state of tobacco materials in an electrically heated tobacco product (eHTP): Evaluation framework and experimental verification","authors":"Lili Fu , Jingmei Han , Qi Zhang , Chuan Liu , Ke Zhang , Yue Zhang , Chunping Wang , Zilong Zhang , Xinyan Jin , Xiaofeng Wang , Le Wang , Ping Lei , Bin Li","doi":"10.1016/j.jaap.2024.106931","DOIUrl":"10.1016/j.jaap.2024.106931","url":null,"abstract":"<div><div>Electrically heated tobacco products (eHTPs) are novel products that could potentially reduce health risks relative to smoking. A series of thermal physico-chemical processes occur in tobacco materials while an eHTP is consumed under designed heating conditions. In order to establish a quantitative characterization of the thermal state of the tobacco materials in eHTPs, this study proposed a universal and systematic framework to evaluate the thermal state of eHTPs, irrespective of the heating technology used by the heating device (e.g., central vs. peripheral, radiation vs. induction, etc). For this purpose, a physical concept of thermal state <span><math><mover><mrow><mi>η</mi><mspace></mspace></mrow><mo>ˆ</mo></mover></math></span>of eHTPs was defined, which indicated the quantities and the compositions of the aerosol released, and a characteristic temperature <span><math><mover><mrow><mi>T</mi></mrow><mo>ˆ</mo></mover></math></span> was also introduced. The framework uses the Pearson correlation to conduct dimensionless treatment on the thermal conversion efficiency of the working eHTPs, which took into account the effective migration of key aerosol components, the release of harmful or potentially harmful constituents (HPHCs), and the oxygen consumption of the thermal processing involved. The framework then defined a combination of datasets corresponding to <span><math><mover><mrow><mi>η</mi></mrow><mo>ˆ</mo></mover></math></span>, which involved 8 key thermophysical indicators, such as the tobacco's thermal mass loss, the oxygen consumption rate and carbon monoxide formation, the release of nicotine, glycerol and total particulate matter, and the release of acetaldehyde and toluene as markers of volatile HPHCs. Under the assumption of a unique relation between <span><math><mover><mrow><mi>η</mi></mrow><mo>ˆ</mo></mover></math></span> and <span><math><mover><mrow><mi>T</mi></mrow><mo>ˆ</mo></mover></math></span>, the numerical function between volume average temperature<span><math><mrow><mspace></mspace><mover><mrow><mi>T</mi></mrow><mo>̅</mo></mover></mrow></math></span> and <span><math><mover><mrow><mi>T</mi></mrow><mo>ˆ</mo></mover></math></span> of the tobacco materials under different heating conditions was obtained by a modified factor method, and the function set <em>f</em>(<span><math><mover><mrow><mi>T</mi></mrow><mo>ˆ</mo></mover></math></span>) was established. When <span><math><mover><mrow><mi>T</mi></mrow><mo>ˆ</mo></mover></math></span> value of 240 ℃ was served as a key reference temperature, its corresponding <span><math><msub><mrow><mover><mrow><mi>η</mi></mrow><mo>ˆ</mo></mover></mrow><mrow><mi>W</mi></mrow></msub></math></span> (substance) was 0.46, the corresponding <span><math><mover><mrow><mi>η</mi></mrow><mo>ˆ</mo></mover></math></span> values for nicotine and glycerol are above 0.85, approaching full release for the two key aerosol substances, with a lower oxygen consumption and the release of HPHCs. Under th","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"186 ","pages":"Article 106931"},"PeriodicalIF":5.8,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143172819","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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