Journal of Analytical and Applied Pyrolysis最新文献_第7页

Investigation of the mechanism and interaction of nitrogen conversion during lignin/glutamic acid co-pyrolysis 木质素/谷氨酸共热解过程中氮转化机理及相互作用的研究

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106795

Hong Tian, Xuan Huang, Bin Zhao, Huang Zhang, Shan Cheng, Lei Liu

Biomass pyrolysis has the potential to be transformed into valuable chemicals and fuels. Nitrogenous chemicals exert a substantial influence on the quality of bio-oil. Studying the impact of lignin on the transformation of nitrogen-containing elements in biomass during biomass pyrolysis is crucial for achieving efficient and effective utilization of biomass resources. In this study, tube furnace experiments, thermogravimetric infrared experiments (TG-FTIR), and gas chromatography-mass spectrometry (Py-GC/MS) were used to investigate the interactions of typical lignins (vanillin and syringol), nitrogenous components (glutamic acid), and the effect of lignin on the pyrolysis gas release of glutamic acid and the pyrolysis products during the co-pyrolysis process. In addition, the impact of lignin on the effect of pyrrolidone formation from glutamic acid was investigated in this study in conjunction with quantum chemical calculations. The experimental findings demonstrated that the co-pyrolysis of lignin and glutamic acid resulted in a reduction in the pyrolysis temperature. This reduction facilitated the release of HCN, NH₃, and CO₂ while notably impeding the formation of nitrogen-containing compounds in the oil. The nitrogen concentration in the pyrolysis oil declined from 97 % to a range of 51.06–79.63 %, and the inhibitory impact decreased as the pyrolysis temperature increased. At an elevated pyrolysis temperature of 800 °C, lignin facilitated the decarboxylation process of glutamic acid, resulting in an increased production of pyrrolidone.Simulation results demonstrated that the lowest energy barrier paths were the dehydration condensation process and the Maillard reaction involving glutamic acid and lignin and their pyrolysis intermediates, with a particular competitive connection between the two pathways. The results explained the interaction mechanism between the two pyrolysis products and provided a fundamental theoretical basis for nitrogen conversion in biomass pyrolysis.

生物质热解有可能转化为有价值的化学品和燃料。含氮化学品对生物油的质量有很大影响。研究生物质热解过程中木质素对生物质中含氮元素转化的影响对于实现生物质资源的高效利用至关重要。本研究采用管式炉实验、热重红外实验（TG-FTIR）和气相色谱-质谱联用仪（Py-GC/MS）研究了典型木质素（香草醛和丁香酚）、含氮成分（谷氨酸）的相互作用，以及木质素在协同热解过程中对谷氨酸和热解产物的热解气体释放的影响。此外，本研究还结合量子化学计算研究了木质素对谷氨酸形成吡咯烷酮的影响。实验结果表明，木质素和谷氨酸共同热解可降低热解温度。温度降低有利于 HCN、NH3 和 CO2 的释放，同时明显阻碍了油中含氮化合物的形成。热解油中的氮浓度从 97% 降至 51.06%-79.63% 之间，随着热解温度的升高，抑制作用也随之减弱。模拟结果表明，能量障碍最低的途径是谷氨酸和木质素及其热解中间产物的脱水缩合过程和马氏反应，这两种途径之间存在特殊的竞争关系。研究结果解释了两种热解产物之间的相互作用机理，为生物质热解过程中的氮转化提供了基本理论依据。

{"title":"Investigation of the mechanism and interaction of nitrogen conversion during lignin/glutamic acid co-pyrolysis","authors":"Hong Tian, Xuan Huang, Bin Zhao, Huang Zhang, Shan Cheng, Lei Liu","doi":"10.1016/j.jaap.2024.106795","DOIUrl":"10.1016/j.jaap.2024.106795","url":null,"abstract":"<div><div>Biomass pyrolysis has the potential to be transformed into valuable chemicals and fuels. Nitrogenous chemicals exert a substantial influence on the quality of bio-oil. Studying the impact of lignin on the transformation of nitrogen-containing elements in biomass during biomass pyrolysis is crucial for achieving efficient and effective utilization of biomass resources. In this study, tube furnace experiments, thermogravimetric infrared experiments (TG-FTIR), and gas chromatography-mass spectrometry (Py-GC/MS) were used to investigate the interactions of typical lignins (vanillin and syringol), nitrogenous components (glutamic acid), and the effect of lignin on the pyrolysis gas release of glutamic acid and the pyrolysis products during the co-pyrolysis process. In addition, the impact of lignin on the effect of pyrrolidone formation from glutamic acid was investigated in this study in conjunction with quantum chemical calculations. The experimental findings demonstrated that the co-pyrolysis of lignin and glutamic acid resulted in a reduction in the pyrolysis temperature. This reduction facilitated the release of HCN, NH<sub>3</sub>, and CO<sub>2</sub> while notably impeding the formation of nitrogen-containing compounds in the oil. The nitrogen concentration in the pyrolysis oil declined from 97 % to a range of 51.06–79.63 %, and the inhibitory impact decreased as the pyrolysis temperature increased. At an elevated pyrolysis temperature of 800 °C, lignin facilitated the decarboxylation process of glutamic acid, resulting in an increased production of pyrrolidone.Simulation results demonstrated that the lowest energy barrier paths were the dehydration condensation process and the Maillard reaction involving glutamic acid and lignin and their pyrolysis intermediates, with a particular competitive connection between the two pathways. The results explained the interaction mechanism between the two pyrolysis products and provided a fundamental theoretical basis for nitrogen conversion in biomass pyrolysis.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106795"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142425728","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Investigation of thermal transport mechanism of silicone-modified phenolic matrix nanocomposites with different pyrolysis degrees 不同热解度硅改性酚醛基纳米复合材料的热传输机理研究

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106793

Jie Xiao, Guodong Fang, Xiaoqiang Qin, Bing Wang, Changqing Hong, Songhe Meng

Polymeric nanocomposites with low thermal conductivity show promising applications for next-generation thermal protection materials used in re-entry vehicles due to their lightweight, high char yield, and excellent ablation-oxidation resistance. However, the thermal conductivity of polymeric nanocomposites varies with the pyrolysis degree of the polymer matrix in aerodynamic environments, which significantly affects thermal protection and structural applications but is challenging to identify experimentally. Herein, non-equilibrium molecular dynamics simulations combined with experiments were implemented to determine the dependence of thermal conductivities on pyrolysis degree and microstructures for polymeric nanocomposites. We further explore the thermal transport mechanism through various contributions to the morphology. The results show that the thermal conductivity of the polymer matrix can be increased by a factor of 4.44 (from 0.27 W/m/K to 1.47 W/m/K) as the pyrolysis degree increases from 0 to 100%, and the thermal conductivity depends nonlinearly on the pyrolysis degree and temperature. Molecular dynamics simulations found that the side chains of the polymer matrix are rapidly scissored with the increasing pyrolysis degrees, and the structural ordering of the residual solids containing sp² hybridization is enhanced, exhibiting graphene-like microtopological features, which reduces phonon scattering and makes thermal transport more efficient. This work provides insight into the linkage between the thermal transport properties and the pyrolysis degree of polymeric nanocomposites, which is valuable for improving the thermal transport performance and modeling ablation response for polymeric nanocomposites.

具有低导热性的聚合物纳米复合材料因其重量轻、炭化率高和优异的抗烧蚀-氧化性能，在重返大气层飞行器使用的下一代热保护材料中具有广阔的应用前景。然而，聚合物纳米复合材料的热导率随聚合物基体在空气动力环境中的热解程度而变化，这对热保护和结构应用有重大影响，但却很难在实验中确定。在此，我们结合实验进行了非平衡分子动力学模拟，以确定聚合物纳米复合材料的热导率与热解程度和微结构的关系。我们进一步探讨了热传输机制对形貌的各种贡献。结果表明，当热解度从 0 增加到 100% 时，聚合物基体的热导率可增加 4.44 倍（从 0.27 W/m/K 增加到 1.47 W/m/K），并且热导率与热解度和温度呈非线性关系。分子动力学模拟发现，聚合物基体的侧链会随着热解度的增加而迅速裂解，含有 sp2 杂化的残余固体的结构有序性增强，呈现出类似石墨烯的微观拓扑特征，从而减少了声子散射，提高了热传输效率。这项研究深入揭示了聚合物纳米复合材料的热传输特性与热解度之间的联系，对改善聚合物纳米复合材料的热传输性能和建立烧蚀响应模型具有重要价值。

{"title":"Investigation of thermal transport mechanism of silicone-modified phenolic matrix nanocomposites with different pyrolysis degrees","authors":"Jie Xiao, Guodong Fang, Xiaoqiang Qin, Bing Wang, Changqing Hong, Songhe Meng","doi":"10.1016/j.jaap.2024.106793","DOIUrl":"10.1016/j.jaap.2024.106793","url":null,"abstract":"<div><div>Polymeric nanocomposites with low thermal conductivity show promising applications for next-generation thermal protection materials used in re-entry vehicles due to their lightweight, high char yield, and excellent ablation-oxidation resistance. However, the thermal conductivity of polymeric nanocomposites varies with the pyrolysis degree of the polymer matrix in aerodynamic environments, which significantly affects thermal protection and structural applications but is challenging to identify experimentally. Herein, non-equilibrium molecular dynamics simulations combined with experiments were implemented to determine the dependence of thermal conductivities on pyrolysis degree and microstructures for polymeric nanocomposites. We further explore the thermal transport mechanism through various contributions to the morphology. The results show that the thermal conductivity of the polymer matrix can be increased by a factor of 4.44 (from 0.27 W/m/K to 1.47 W/m/K) as the pyrolysis degree increases from 0 to 100%, and the thermal conductivity depends nonlinearly on the pyrolysis degree and temperature. Molecular dynamics simulations found that the side chains of the polymer matrix are rapidly scissored with the increasing pyrolysis degrees, and the structural ordering of the residual solids containing sp<sup>2</sup> hybridization is enhanced, exhibiting graphene-like microtopological features, which reduces phonon scattering and makes thermal transport more efficient. This work provides insight into the linkage between the thermal transport properties and the pyrolysis degree of polymeric nanocomposites, which is valuable for improving the thermal transport performance and modeling ablation response for polymeric nanocomposites.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106793"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142425790","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Insight into evolution characteristics of pyrolysis products of HLH and HL coal with Py-VUVPI-MS and DFT 利用 Py-VUVPI-MS 和 DFT 深入了解 HLH 和 HL 煤热解产物的演变特征

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106829

Zhiwei Shi , Zhi Zhang , Huiyu Han , Xinfu He , Yagang Zhang , Anning Zhou , Lijun Jin , Haoquan Hu

To achieve a comprehensive understanding of the influence of chemical structure on the evolution characteristics of coal pyrolysis products, pyrolysis reaction of two kinds of low rank coal (Huolinhe and Huangling coal) were investigated with pyrolysis-vacuum ultraviolet photoionization mass spectrometry (Py-VUVPI-MS). The soft ionized mass spectral detection can provide evolved information of original pyrolysis product. The chemical structure of coal samples was characterized by solid-state ¹³C NMR, indicating HLH coal with more branched chain and longer aliphatic chain structure. The bond dissociation enthalpies (BDE) of β-C_al-C_al and β-C_al-O within model compounds were obtained with density functional theory. The difference of peak temperature with maximum evolution was collected to investigate the effect of the chemical environment on evolution behavior of pyrolysis products. The results reveal that branched and long aliphatic side-chains can reduces BDE of β-C_al-C_al and β-C_al-O, resulting in the lower peak temperature of pyrolysis products derived from HLH coal. Substituent groups (such as alkyl and hydroxyl groups) attached on the aromatic rings can reduce peak temperatures. Moreover, the effects of the different substituted position on the aromatic ring of the methyl group presented on differences of the BDE. An increase in aromatic ring size correlates with a certain degree of reduction in BDE for β-C_al-C_al; consequently, peak temperature of pyrolysis products with larger aromatic rings is lower. The pyrolysis behavior of coal were discussed based on the experimental observations and theoretical calculation, which are beneficial to understand the reaction route and mechanism of coal pyrolysis.

为全面了解化学结构对煤热解产物演化特征的影响，采用热解-真空紫外光离子化质谱（Py-VUVPI-MS）对两种低阶煤（霍林河煤和黄陵煤）的热解反应进行了研究。软电离质谱检测可提供原始热解产物的进化信息。固态 13C NMR 对煤样的化学结构进行了表征，结果表明 HLH 煤具有更多的支链和更长的脂肪族链结构。利用密度泛函理论得到了模型化合物中 β-Cal-Cal 和 β-Cal-O 的键解离焓（BDE）。收集了峰值温度与最大演化温度之差，以研究化学环境对热解产物演化行为的影响。结果表明，支链和长脂肪族侧链可降低β-Cal-Cal 和 β-Cal-O的BDE，从而导致HLH煤热解产物的峰值温度降低。芳香环上的取代基（如烷基和羟基）可降低峰值温度。此外，甲基在芳香环上的不同取代位置也会对溴化二苯醚的差异产生影响。芳香环尺寸的增加与 β-Cal-Cal 的 BDE 降低程度相关；因此，芳香环较大的热解产物的峰值温度较低。基于实验观察和理论计算对煤的热解行为进行了讨论，有助于理解煤热解的反应路线和机理。

{"title":"Insight into evolution characteristics of pyrolysis products of HLH and HL coal with Py-VUVPI-MS and DFT","authors":"Zhiwei Shi , Zhi Zhang , Huiyu Han , Xinfu He , Yagang Zhang , Anning Zhou , Lijun Jin , Haoquan Hu","doi":"10.1016/j.jaap.2024.106829","DOIUrl":"10.1016/j.jaap.2024.106829","url":null,"abstract":"<div><div>To achieve a comprehensive understanding of the influence of chemical structure on the evolution characteristics of coal pyrolysis products, pyrolysis reaction of two kinds of low rank coal (Huolinhe and Huangling coal) were investigated with pyrolysis-vacuum ultraviolet photoionization mass spectrometry (Py-VUVPI-MS). The soft ionized mass spectral detection can provide evolved information of original pyrolysis product. The chemical structure of coal samples was characterized by solid-state <sup>13</sup>C NMR, indicating HLH coal with more branched chain and longer aliphatic chain structure. The bond dissociation enthalpies (BDE) of β-C<sub>al</sub>-C<sub>al</sub> and β-C<sub>al</sub>-O within model compounds were obtained with density functional theory. The difference of peak temperature with maximum evolution was collected to investigate the effect of the chemical environment on evolution behavior of pyrolysis products. The results reveal that branched and long aliphatic side-chains can reduces BDE of β-C<sub>al</sub>-C<sub>al</sub> and β-C<sub>al</sub>-O, resulting in the lower peak temperature of pyrolysis products derived from HLH coal. Substituent groups (such as alkyl and hydroxyl groups) attached on the aromatic rings can reduce peak temperatures. Moreover, the effects of the different substituted position on the aromatic ring of the methyl group presented on differences of the BDE. An increase in aromatic ring size correlates with a certain degree of reduction in BDE for β-C<sub>al</sub>-C<sub>al</sub>; consequently, peak temperature of pyrolysis products with larger aromatic rings is lower. The pyrolysis behavior of coal were discussed based on the experimental observations and theoretical calculation, which are beneficial to understand the reaction route and mechanism of coal pyrolysis.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106829"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Adsorption of dibenzofuran by modified biochar derived from microwave gasification: Impact factors and adsorption mechanism 微波气化产生的改性生物炭对二苯并呋喃的吸附：影响因素和吸附机理

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106831

Jiyun Ren , Yong Zhang , Hui Wang , Xiaoming Huang , Xiaoling Jin , Kai Zhang , Ruiyu Li , Kaixuan Yang , Yang Yue , Lei Deng , Defu Che

Dioxins, emanating from the waste incineration, constitutes an organic pollutant that poses considerable risks to the human health and environment. In this study, the corn straw char (CSC) and oak char (OC) derived from the electric heating or microwave gasification, and the coconut-shell activated carbon (AC) are employed as absorbents for the adsorption of dibenzofuran (DBF, dioxins model compound). Characterization techniques, including BET, X-ray CT, SEM-EDS, FTIR, and XPS, are performed to identify the DBF adsorption mechanism on the biochar. The results show that the biochar prepared by the microwave gasification has a more well-developed pore structure than that of the electric heating gasification. The higher porosity (16.94 %) and lower mineral content (1.75 %) are responsible for the effective adsorption of DBF onto AC. The adsorption capacity of CSC is proportional to the modified concentration of KOH. It is mainly ascribed to the decrement of carboxyl and lactone groups and the enhancement of alkaline functional groups on the biochar surface, which augments the hydrophobicity and π–π electron donor–acceptor (EDA) interaction. Instead, DBF adsorption capacity on the biochar is adversely affected by the HNO₃ modification. For all biochar samples, the corresponding maximum adsorption ratios are AC (87.11 %) > KOH-modified CSC (77.14 %) > unmodified CSC (49.11 %) > unmodified OC (39.70 %) > HNO₃-modified CSC (36.09 %). The adsorption mechanisms of DBF on the gasified biochar encompass the pore filling, hydrophobicity, and π–π EDA interaction. A desirable adsorption capacity of DBF on the biochar prepared by the microwave gasification is attainable through augmenting the specific surface area while diminishing the oxygen-containing groups of the surface simultaneously.

垃圾焚烧过程中产生的二恶英是一种有机污染物，对人类健康和环境造成了相当大的危害。本研究采用电加热或微波气化产生的玉米秸秆炭（CSC）和橡木炭（OC）以及椰壳活性炭（AC）作为吸附二苯并呋喃（DBF，二恶英模型化合物）的吸附剂。通过 BET、X 射线 CT、SEM-EDS、FTIR 和 XPS 等表征技术来确定 DBF 在生物炭上的吸附机理。结果表明，微波气化制备的生物炭比电加热气化制备的生物炭具有更发达的孔隙结构。较高的孔隙率（16.94 %）和较低的矿物含量（1.75 %）是 DBF 在 AC 上被有效吸附的原因。CSC 的吸附能力与改良的 KOH 浓度成正比。这主要是由于生物炭表面的羧基和内酯基减少，碱性官能团增加，从而增强了疏水性和π-π电子供体-受体（EDA）相互作用。相反，生物炭上的 DBF 吸附能力受到 HNO3 改性的不利影响。在所有生物炭样品中，相应的最大吸附率分别为：AC（87.11 %）>；KOH 改性 CSC（77.14 %）>；未改性 CSC（49.11 %）>；未改性 OC（39.70 %）>；HNO3 改性 CSC（36.09 %）。DBF 在气化生物炭上的吸附机理包括孔隙填充、疏水性和 π-π EDA 相互作用。通过增加比表面积，同时减少表面的含氧基团，微波气化制备的生物炭可以达到理想的 DBF 吸附能力。

{"title":"Adsorption of dibenzofuran by modified biochar derived from microwave gasification: Impact factors and adsorption mechanism","authors":"Jiyun Ren , Yong Zhang , Hui Wang , Xiaoming Huang , Xiaoling Jin , Kai Zhang , Ruiyu Li , Kaixuan Yang , Yang Yue , Lei Deng , Defu Che","doi":"10.1016/j.jaap.2024.106831","DOIUrl":"10.1016/j.jaap.2024.106831","url":null,"abstract":"<div><div>Dioxins, emanating from the waste incineration, constitutes an organic pollutant that poses considerable risks to the human health and environment. In this study, the corn straw char (CSC) and oak char (OC) derived from the electric heating or microwave gasification, and the coconut-shell activated carbon (AC) are employed as absorbents for the adsorption of dibenzofuran (DBF, dioxins model compound). Characterization techniques, including BET, X-ray CT, SEM-EDS, FTIR, and XPS, are performed to identify the DBF adsorption mechanism on the biochar. The results show that the biochar prepared by the microwave gasification has a more well-developed pore structure than that of the electric heating gasification. The higher porosity (16.94 %) and lower mineral content (1.75 %) are responsible for the effective adsorption of DBF onto AC. The adsorption capacity of CSC is proportional to the modified concentration of KOH. It is mainly ascribed to the decrement of carboxyl and lactone groups and the enhancement of alkaline functional groups on the biochar surface, which augments the hydrophobicity and π–π electron donor–acceptor (EDA) interaction. Instead, DBF adsorption capacity on the biochar is adversely affected by the HNO<sub>3</sub> modification. For all biochar samples, the corresponding maximum adsorption ratios are AC (87.11 %) > KOH-modified CSC (77.14 %) > unmodified CSC (49.11 %) > unmodified OC (39.70 %) > HNO<sub>3</sub>-modified CSC (36.09 %). The adsorption mechanisms of DBF on the gasified biochar encompass the pore filling, hydrophobicity, and π–π EDA interaction. A desirable adsorption capacity of DBF on the biochar prepared by the microwave gasification is attainable through augmenting the specific surface area while diminishing the oxygen-containing groups of the surface simultaneously.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106831"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Catalytic pyrolysis of biodegradable plastic in CO2 atmosphere using MSW incinerator bottom ash for PLA monomer recovery 利用城市生活垃圾焚烧炉底灰在二氧化碳气氛中催化热解生物可降解塑料以回收聚乳酸单体

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106839

Shuting Fu , Doeun Choi , Jechan Lee

This study proposes a method for recovering value-added monomers from abandoned biodegradable plastics such as used biodegradable straws (UBSs) by utilizing a catalyst made of bottom ash generated from municipal solid waste (MSW) incinerators. The MSW-derived bottom ash (MSW-BA) catalyst primarily comprises alkaline metal oxides such as CaO (58.88 wt%). Thermogravimetric and single-shot pyrolysis analyses show that polylactic acid (PLA) monomers—lactide and lactic acid—are the main products of UBS pyrolysis. We conducted catalytic pyrolysis of UBS at 500 °C under different atmospheres (N₂ and CO₂), with and without the MSW-BA catalyst. Compared with non-catalytic pyrolysis, the MSW-BA catalyst-based pyrolysis significantly increased the yield of PLA monomers in both N₂ and CO₂ environments. This is because the base sites present on the MSW-BA catalyst promoted the polymeric bond cleavage of PLA. The MSW-BA catalyst in CO₂ achieved the highest recovery yield of PLA monomers (20.84 wt% per feedstock mass basis), which was approximately 17.75 % higher than that during non-catalytic UBS pyrolysis. The base sites present on the MSW-BA catalyst promoted polymeric bond cleavage of PLA, and the base-catalyzed pyrolysis of PLA was enhanced by the more reactive cleavage of the bond linkages in the presence of CO₂. The proposed approach not only reuses biodegradable plastic waste but also utilizes the MSW treatment byproducts.

本研究提出了一种利用城市固体废物（MSW）焚化炉产生的底灰为催化剂，从废弃的可生物降解塑料（如废旧可生物降解吸管（UBS））中回收增值单体的方法。城市固体废物产生的底灰（MSW-BA）催化剂主要由碱性金属氧化物组成，如 CaO（58.88 wt%）。热重分析和单次热解分析表明，聚乳酸（PLA）单体--内酰胺和乳酸--是 UBS 热解的主要产物。我们在不同的气氛（N2 和 CO2）下，在使用或不使用 MSW-BA 催化剂的情况下，在 500 °C 下对 UBS 进行了催化热解。与非催化热解相比，基于 MSW-BA 催化剂的热解在 N2 和 CO2 环境下都显著提高了聚乳酸单体的产量。这是因为 MSW-BA 催化剂上的碱基位点促进了聚乳酸聚合物键的裂解。在二氧化碳环境中，MSW-BA 催化剂获得了最高的聚乳酸单体回收率（20.84 wt%（按原料质量计）），比非催化 UBS 热解过程中的回收率高出约 17.75%。MSW-BA 催化剂上的碱基位点促进了聚乳酸聚合物键的裂解，在二氧化碳存在的情况下，碱催化的聚乳酸热解因键链的裂解反应更加活跃而得到加强。所提出的方法不仅重复利用了可生物降解的塑料废弃物，而且还利用了城市固体废弃物处理的副产品。

{"title":"Catalytic pyrolysis of biodegradable plastic in CO2 atmosphere using MSW incinerator bottom ash for PLA monomer recovery","authors":"Shuting Fu , Doeun Choi , Jechan Lee","doi":"10.1016/j.jaap.2024.106839","DOIUrl":"10.1016/j.jaap.2024.106839","url":null,"abstract":"<div><div>This study proposes a method for recovering value-added monomers from abandoned biodegradable plastics such as used biodegradable straws (UBSs) by utilizing a catalyst made of bottom ash generated from municipal solid waste (MSW) incinerators. The MSW-derived bottom ash (MSW-BA) catalyst primarily comprises alkaline metal oxides such as CaO (58.88 wt%). Thermogravimetric and single-shot pyrolysis analyses show that polylactic acid (PLA) monomers—lactide and lactic acid—are the main products of UBS pyrolysis. We conducted catalytic pyrolysis of UBS at 500 °C under different atmospheres (N<sub>2</sub> and CO<sub>2</sub>), with and without the MSW-BA catalyst. Compared with non-catalytic pyrolysis, the MSW-BA catalyst-based pyrolysis significantly increased the yield of PLA monomers in both N<sub>2</sub> and CO<sub>2</sub> environments. This is because the base sites present on the MSW-BA catalyst promoted the polymeric bond cleavage of PLA. The MSW-BA catalyst in CO<sub>2</sub> achieved the highest recovery yield of PLA monomers (20.84 wt% per feedstock mass basis), which was approximately 17.75 % higher than that during non-catalytic UBS pyrolysis. The base sites present on the MSW-BA catalyst promoted polymeric bond cleavage of PLA, and the base-catalyzed pyrolysis of PLA was enhanced by the more reactive cleavage of the bond linkages in the presence of CO<sub>2</sub>. The proposed approach not only reuses biodegradable plastic waste but also utilizes the MSW treatment byproducts.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106839"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Catalytic ethanolysis of Xiaojihan subbituminous coal to platform chemicals enhanced by pre-oxidation with ozone 通过臭氧预氧化增强小纪汗亚烟煤催化乙醇分解制备平台化学品的能力

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106782

Qi-Yang Zhu , Yong Gao , Miao-Miao Jia , Xia-Long Li , Guang-Hui Liu , Yan-Jun Li , Yu-Hong Kang , Jin-Jun Bai , Chen Shi , Xian-Yong Wei

Xiaojihan subbituminous coal (XSBC) was pre-oxidized by ozone to prepare oxidized XSBC (OXSBC). Then, the ethanolysis was conducted on OXSBC at 300 °C under an initial nitrogen pressure (INP) of 1 MPa for 2 h. On this basis, the influences of pre-oxidation conditions on the content of oxygen-containing functional groups and the yield of soluble portion (SP) from the ethanolysis of XSBC and OXSBC were explored. The research results show that the yield of SP from the OXSBC ethanolysis is higher than that from the XSBC ethanolysis, and the highest yield of SP from the OXSBC ethanolysis reaches 24.9 wt% at 50 °C for 3 h, an increase of 80.4 % compared to the yield of SP from the XSBC ethanolysis. Besides, the magnetic nanosphere Co-CuFe₂O₄ catalyst, prepared by adopting the one-pot hydrothermal method, was applied to the catalytic ethanolysis (CE) of OXSBC3 at 300 °C, 1 MPa INP, and 2 h. The catalyst is noticeably active in the CE of OXSBC3, as it promotes the yields of SP and oxygen-containing organic compounds obtained from the OXSBC3 ethanolysis from 24.9 wt% and 76.25 mg g⁻¹ to 42.8 wt% and 204.16 mg g⁻¹, respectively. The CE of the model compound demonstrates that ethanol is activated by Co-CuFe₂O₄ to release H⁺, H^-, and ⁺CH₂CH₃, which play a crucial role in the conversion of benzyloxybenzene. This study provides a novel approach for acquiring value-added organic chemicals from low-rank coals.

采用臭氧对小纪汗亚烟煤（XSBC）进行预氧化，制备出氧化XSBC（OXSBC）。然后，在初始氮气压力（INP）为 1 MPa 的条件下，于 300 °C 下对 OXSBC 进行乙醇分解 2 小时。在此基础上，探讨了预氧化条件对 XSBC 和 OXSBC 乙解过程中含氧官能团含量和可溶性部分（SP）产率的影响。研究结果表明，OXSBC乙醇解的可溶性部分（SP）产率高于XSBC乙醇解的可溶性部分（SP）产率，其中在50 °C、3 h的条件下，OXSBC乙醇解的可溶性部分（SP）产率最高，达到24.9 wt%，比XSBC乙醇解的可溶性部分（SP）产率提高了80.4%。此外，采用一锅水热法制备的磁性纳米球 Co-CuFe2O4 催化剂被用于 OXSBC3 在 300 ℃、1 MPa INP 和 2 h 条件下的催化乙醇分解（CE）。该催化剂在 OXSBC3 的催化乙醇分解过程中具有明显的活性，它使 OXSBC3 乙醇分解得到的 SP 和含氧有机化合物的产率分别从 24.9 wt% 和 76.25 mg g-1 提高到 42.8 wt% 和 204.16 mg g-1。模型化合物的 CE 表明，乙醇被 Co-CuFe2O4 激活后释放出 H+、H- 和 +CH2CH3，它们在苄氧基苯的转化过程中起着至关重要的作用。这项研究为从低阶煤中获取高附加值有机化学品提供了一种新方法。

{"title":"Catalytic ethanolysis of Xiaojihan subbituminous coal to platform chemicals enhanced by pre-oxidation with ozone","authors":"Qi-Yang Zhu , Yong Gao , Miao-Miao Jia , Xia-Long Li , Guang-Hui Liu , Yan-Jun Li , Yu-Hong Kang , Jin-Jun Bai , Chen Shi , Xian-Yong Wei","doi":"10.1016/j.jaap.2024.106782","DOIUrl":"10.1016/j.jaap.2024.106782","url":null,"abstract":"<div><div>Xiaojihan subbituminous coal (XSBC) was pre-oxidized by ozone to prepare oxidized XSBC (OXSBC). Then, the ethanolysis was conducted on OXSBC at 300 °C under an initial nitrogen pressure (INP) of 1 MPa for 2 h. On this basis, the influences of pre-oxidation conditions on the content of oxygen-containing functional groups and the yield of soluble portion (SP) from the ethanolysis of XSBC and OXSBC were explored. The research results show that the yield of SP from the OXSBC ethanolysis is higher than that from the XSBC ethanolysis, and the highest yield of SP from the OXSBC ethanolysis reaches 24.9 wt% at 50 °C for 3 h, an increase of 80.4 % compared to the yield of SP from the XSBC ethanolysis. Besides, the magnetic nanosphere Co-CuFe<sub>2</sub>O<sub>4</sub> catalyst, prepared by adopting the one-pot hydrothermal method, was applied to the catalytic ethanolysis (CE) of OXSBC3 at 300 °C, 1 MPa INP, and 2 h. The catalyst is noticeably active in the CE of OXSBC3, as it promotes the yields of SP and oxygen-containing organic compounds obtained from the OXSBC3 ethanolysis from 24.9 wt% and 76.25 mg g<sup>−1</sup> to 42.8 wt% and 204.16 mg g<sup>−1</sup>, respectively. The CE of the model compound demonstrates that ethanol is activated by Co-CuFe<sub>2</sub>O<sub>4</sub> to release H<sup>+</sup>, H<sup>-</sup>, and <sup>+</sup>CH<sub>2</sub>CH<sub>3</sub>, which play a crucial role in the conversion of benzyloxybenzene. This study provides a novel approach for acquiring value-added organic chemicals from low-rank coals.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106782"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142425788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Laboratory-scale simulation study of pyrolysis process in a fixed-bed gasifier for municipal solid waste pellets: Effects of temperature distribution and residence time 城市固体废物颗粒在固定床气化炉中热解过程的实验室规模模拟研究：温度分布和停留时间的影响

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-10-01 DOI: 10.1016/j.jaap.2024.106832

Zichao Hu , Longfei Tang , Peipei Gao , Bin Wang , Chang Zhang , Weitong Pan , Lu Ding , Xueli Chen , Fuchen Wang

In this study, stepwise heating pyrolysis was designed to simulate the pyrolysis process of municipal solid waste (MSW) pellet in an updraft fixed bed gasifier at a laboratory scale. Differences in pyrolysis product between fixed bed stepwise heating pyrolysis (FBS, ranging from 300 °C to 800 °C) and continuous heating pyrolysis (FBC, maintained at 800 °C) were revealed. The impact of residence time at various temperature ranges on MSW pyrolysis was also investigated. Results indicated that compared to FBC, the gas yield of FBS decreased by 30.74 %, while its liquid yield increased by 11.96 %. It was primarily due to the lower heating rate reduced the secondary conversion of aliphatic hydrocarbons, oxygenated compounds, and monoaromatic hydrocarbons (MAHs) within liquid products. In addition, the composition of MSW pyrolysis products was changed by adjusting the residence time. Maintaining a uniform residence time of 5 min for MSW pellets at each temperature was considered optimal for gas yield, which was mainly attributed to the enhanced cracking of long-chain aliphatic and polycondensation of MAHs and polycyclic aromatic hydrocarbons (PAHs). Besides, the volatiles (C- and O-containing compounds) of the char were almost completely released. The underlying influence mechanism of residence time on the pyrolysis behavior of MSW was also proposed, which could provide insights for the implementation of MSW gasification.

本研究设计了分步加热热解，在实验室规模上模拟了城市固体废物（MSW）颗粒在上升气流固定床气化炉中的热解过程。结果表明，固定床分步加热热解（FBS，温度范围为 300 ℃ 至 800 ℃）和连续加热热解（FBC，温度保持在 800 ℃）的热解产物存在差异。此外，还研究了在不同温度范围内的停留时间对城市固体废物热解的影响。结果表明，与 FBC 相比，FBS 的气体产量减少了 30.74%，而液体产量增加了 11.96%。这主要是由于较低的加热速率减少了液体产品中脂肪族碳氢化合物、含氧化合物和单芳烃（MAHs）的二次转化。此外，还通过调整停留时间来改变城市固体废物热解产物的成分。在每个温度下，保持 MSW 粒子 5 分钟的均匀停留时间被认为是气体产量的最佳值，这主要归功于长链脂肪族的裂解以及 MAHs 和多环芳烃 (PAHs) 的缩聚作用的增强。此外，炭的挥发物（含 C 和 O 的化合物）几乎完全释放。研究还提出了停留时间对城市固体废物热解行为的潜在影响机理，为城市固体废物气化的实施提供了启示。

{"title":"Laboratory-scale simulation study of pyrolysis process in a fixed-bed gasifier for municipal solid waste pellets: Effects of temperature distribution and residence time","authors":"Zichao Hu , Longfei Tang , Peipei Gao , Bin Wang , Chang Zhang , Weitong Pan , Lu Ding , Xueli Chen , Fuchen Wang","doi":"10.1016/j.jaap.2024.106832","DOIUrl":"10.1016/j.jaap.2024.106832","url":null,"abstract":"<div><div>In this study, stepwise heating pyrolysis was designed to simulate the pyrolysis process of municipal solid waste (MSW) pellet in an updraft fixed bed gasifier at a laboratory scale. Differences in pyrolysis product between fixed bed stepwise heating pyrolysis (FBS, ranging from 300 °C to 800 °C) and continuous heating pyrolysis (FBC, maintained at 800 °C) were revealed. The impact of residence time at various temperature ranges on MSW pyrolysis was also investigated. Results indicated that compared to FBC, the gas yield of FBS decreased by 30.74 %, while its liquid yield increased by 11.96 %. It was primarily due to the lower heating rate reduced the secondary conversion of aliphatic hydrocarbons, oxygenated compounds, and monoaromatic hydrocarbons (MAHs) within liquid products. In addition, the composition of MSW pyrolysis products was changed by adjusting the residence time. Maintaining a uniform residence time of 5 min for MSW pellets at each temperature was considered optimal for gas yield, which was mainly attributed to the enhanced cracking of long-chain aliphatic and polycondensation of MAHs and polycyclic aromatic hydrocarbons (PAHs). Besides, the volatiles (C- and O-containing compounds) of the char were almost completely released. The underlying influence mechanism of residence time on the pyrolysis behavior of MSW was also proposed, which could provide insights for the implementation of MSW gasification.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106832"},"PeriodicalIF":5.8,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Valorizing lignocellulose into aromatic compounds via oxidative catalytic fractionation and transformation strategy catalyzed by polyoxometalates 通过氧化催化分馏将木质纤维素转化为芳香族化合物，以及在多氧金属酸盐催化下的转化策略

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-09-25 DOI: 10.1016/j.jaap.2024.106786

Mingfei Li , Shumin Wang , Haoyu Deng , Junyou Shi , Dan Zhang , Wenbiao Xu

Utilizing renewable resources as substitutes for fossil resources is a crucial pathway towards achieving sustainability, with biomass conversion being a significant avenue. Catalytic fractionation of lignocellulose represents an effective approach to biomass conversion, wherein lignin is selectively separated from lignocellulose and depolymerized into high-value aromatic monomers within the reaction system. However, existing technologies face challenges such as low product selectivity and difficult separation. Herein, we employ oxidative catalytic fractionation (OCF) using polyoxometalates (POMs) as catalysts and a methanol/water mixture as solvent to directly oxidize and catalyze lignin in pine wood lignocellulose into aromatic compounds under an O₂ atmosphere, while preserving cellulose for subsequent utilization. The process yields up to 22.5 % aromatic monomers, with vanillin and methyl vanillate as the main products (calculated based on Klason lignin). Our approach provides a novel perspective for achieving highly selective oxidative fractionation and depolymerization of lignin, thus contributing to the valorization of lignocellulose.

利用可再生资源替代化石资源是实现可持续发展的重要途径，其中生物质转化是一个重要的途径。木质纤维素的催化分馏是生物质转化的一种有效方法，在这种方法中，木质素被选择性地从木质纤维素中分离出来，并在反应系统中解聚成高价值的芳香族单体。然而，现有技术面临着产品选择性低和分离困难等挑战。在此，我们采用氧化催化分馏（OCF）技术，以聚氧金属盐（POMs）为催化剂，甲醇/水混合物为溶剂，在氧气环境下直接氧化并催化松木木质纤维素中的木质素为芳香族化合物，同时保留纤维素以供后续利用。该工艺的芳香族单体产量高达 22.5%，主要产品为香兰素和香兰酸甲酯（根据克拉松木素计算）。我们的方法为实现木质素的高选择性氧化分馏和解聚提供了一个新的视角，从而有助于木质纤维素的价值提升。

{"title":"Valorizing lignocellulose into aromatic compounds via oxidative catalytic fractionation and transformation strategy catalyzed by polyoxometalates","authors":"Mingfei Li , Shumin Wang , Haoyu Deng , Junyou Shi , Dan Zhang , Wenbiao Xu","doi":"10.1016/j.jaap.2024.106786","DOIUrl":"10.1016/j.jaap.2024.106786","url":null,"abstract":"<div><div>Utilizing renewable resources as substitutes for fossil resources is a crucial pathway towards achieving sustainability, with biomass conversion being a significant avenue. Catalytic fractionation of lignocellulose represents an effective approach to biomass conversion, wherein lignin is selectively separated from lignocellulose and depolymerized into high-value aromatic monomers within the reaction system. However, existing technologies face challenges such as low product selectivity and difficult separation. Herein, we employ oxidative catalytic fractionation (OCF) using polyoxometalates (POMs) as catalysts and a methanol/water mixture as solvent to directly oxidize and catalyze lignin in pine wood lignocellulose into aromatic compounds under an O<sub>2</sub> atmosphere, while preserving cellulose for subsequent utilization. The process yields up to 22.5 % aromatic monomers, with vanillin and methyl vanillate as the main products (calculated based on Klason lignin). Our approach provides a novel perspective for achieving highly selective oxidative fractionation and depolymerization of lignin, thus contributing to the valorization of lignocellulose.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106786"},"PeriodicalIF":5.8,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142327174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Feasibility and recovery efficiency of in-situ shale oil conversion in fractured reservoirs via steam heating: Based on a coupled thermo-flow-chemical model 通过蒸汽加热在断裂储层中就地转化页岩油的可行性和采收效率：基于热流-化学耦合模型

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-09-25 DOI: 10.1016/j.jaap.2024.106787

Zhaobin Zhang , Zhuoran Xie , Maryelin Josefina Briceño Montilla , Yuxuan Li , Tao Xu , Shouding Li , Xiao Li

Shale oil is a type of liquid hydrocarbon obtained through the pyrolysis of organic matter such as kerogen in oil shale reservoirs. Effective extraction of shale oil can significantly alleviate the pressure on oil supply. Among the various methods proposed for shale oil extraction, in-situ conversion of shale oil through high-temperature steam heating is a promising technique. This study employs a newly developed thermo-flow-chemical numerical simulator to establish a heterogeneous geological model and provides a detailed description of the evolution of different components within the shale oil reservoir during the in-situ conversion process. Additionally, the study thoroughly analyzes the role of high-permeability channels, such as fractures, in fluid transport and heat transfer during this process. In comparison with homogeneous reservoirs, fractures play a controlling role in the transport of steam. After injection, steam forms a preferential transport path between the heating well and the production well through the fractures. Subsequent injected steam will preferentially travel through this path, leading to faster heating of the reservoir. However, the uneven distribution of fractures may result in incomplete pyrolysis of the organic matter within the reservoir. Additionally, we found that the producing pressure and the steam injection rate significantly affect the pyrolysis of kerogen and the production of oil and gas. Both excessively low producing pressure and excessively high steam injection rate are detrimental to shale oil extraction. Based on these findings, this study aims to develop more rational heating strategies for reservoirs with different characteristics.

页岩油是一种通过热解油页岩储层中的有机物（如角质）而获得的液态碳氢化合物。有效开采页岩油可以大大缓解石油供应压力。在提出的各种页岩油开采方法中，通过高温蒸汽加热原位转化页岩油是一种很有前景的技术。本研究利用新开发的热流化学数值模拟器建立了一个异质地质模型，详细描述了页岩油储层中不同成分在原位转化过程中的演变。此外，研究还深入分析了裂缝等高渗透通道在这一过程中的流体输送和热量传递作用。与均质储层相比，裂缝在蒸汽输送中起着控制作用。注入蒸汽后，蒸汽通过裂缝在加热井和生产井之间形成优先输送路径。随后注入的蒸汽将优先通过该路径，从而加快储层的加热速度。然而，裂缝分布不均可能导致储层内的有机物热解不完全。此外，我们还发现，生产压力和蒸汽注入率对角质热解以及油气产量有很大影响。过低的开采压力和过高的蒸汽注入率都不利于页岩油的开采。基于这些发现，本研究旨在为具有不同特征的储层制定更合理的加热策略。

{"title":"Feasibility and recovery efficiency of in-situ shale oil conversion in fractured reservoirs via steam heating: Based on a coupled thermo-flow-chemical model","authors":"Zhaobin Zhang , Zhuoran Xie , Maryelin Josefina Briceño Montilla , Yuxuan Li , Tao Xu , Shouding Li , Xiao Li","doi":"10.1016/j.jaap.2024.106787","DOIUrl":"10.1016/j.jaap.2024.106787","url":null,"abstract":"<div><div>Shale oil is a type of liquid hydrocarbon obtained through the pyrolysis of organic matter such as kerogen in oil shale reservoirs. Effective extraction of shale oil can significantly alleviate the pressure on oil supply. Among the various methods proposed for shale oil extraction, in-situ conversion of shale oil through high-temperature steam heating is a promising technique. This study employs a newly developed thermo-flow-chemical numerical simulator to establish a heterogeneous geological model and provides a detailed description of the evolution of different components within the shale oil reservoir during the in-situ conversion process. Additionally, the study thoroughly analyzes the role of high-permeability channels, such as fractures, in fluid transport and heat transfer during this process. In comparison with homogeneous reservoirs, fractures play a controlling role in the transport of steam. After injection, steam forms a preferential transport path between the heating well and the production well through the fractures. Subsequent injected steam will preferentially travel through this path, leading to faster heating of the reservoir. However, the uneven distribution of fractures may result in incomplete pyrolysis of the organic matter within the reservoir. Additionally, we found that the producing pressure and the steam injection rate significantly affect the pyrolysis of kerogen and the production of oil and gas. Both excessively low producing pressure and excessively high steam injection rate are detrimental to shale oil extraction. Based on these findings, this study aims to develop more rational heating strategies for reservoirs with different characteristics.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106787"},"PeriodicalIF":5.8,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142327175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Microwave plasma conversion of food waste using carbon foam: Production of heteroatom-doped graphene and combustible gas 利用泡沫碳对食物垃圾进行微波等离子体转化：生产掺杂杂原子的石墨烯和可燃气体

IF 5.8 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2024-09-24 DOI: 10.1016/j.jaap.2024.106785

Zhiyang Liu , Kun Chen , Rui Li, Weining Li, Minghui Gong, Xiaoqi Liu, Wei Xia, Dong Liu

The mass production of food waste (FW) has a terrible impact on the environment, but with proper treatment, FW can be transformed into a new resource. Currently, thermal conversion (especially incineration) has been the most common and efficient means of handling FW, but it also entails negative impacts, such as high carbon emissions and lower added value. In this study, a new high-efficiency thermal conversion process is proposed that uses carbon foams to induce the formation of microwave plasma (MP), which generates very high final temperatures to enable the direct conversion of FW into combustible gases and high-value-added heteroatom-doped microwave plasma graphene (HMPG) in 5–20 s. This work investigated the optimal carbonization temperature of the melamine sponge (carbon foam precursor) and the effect of microwave plasma reaction duration on the distribution of the gas products and the properties of HMPG, and HMPG was characterized in detail by Raman spectroscopy, X-ray diffraction, scanning electron microscope, etc. Ultimately, HMPG was tested in potassium ion battery anodes for evaluation of its energy storage potential, and the results showed that the capacities were able to reach ∼270 mAh g⁻¹ at 50 mA g⁻¹ after 60 cycles.

食物垃圾（FW）的大量产生对环境造成了可怕的影响，但如果处理得当，食物垃圾可以转化为新的资源。目前，热转化（尤其是焚烧）是处理厨余垃圾最常见、最有效的方法，但它也会带来负面影响，如碳排放量高、附加值低等。本研究提出了一种新型高效热转化工艺，利用碳泡沫诱导微波等离子体（MP）的形成，从而产生极高的最终温度，在 5-20 秒内将 FW 直接转化为可燃气体和高附加值的杂原子掺杂微波等离子体石墨烯（HMPG）。这项工作研究了三聚氰胺海绵（碳泡沫前体）的最佳碳化温度以及微波等离子体反应持续时间对气体产物分布和 HMPG 性能的影响，并通过拉曼光谱、X 射线衍射、扫描电子显微镜等对 HMPG 进行了详细表征。最后，在钾离子电池阳极中测试了 HMPG 的储能潜力，结果表明在 50 mA g-1 的条件下，循环 60 次后容量可达 ∼270 mAh g-1。

{"title":"Microwave plasma conversion of food waste using carbon foam: Production of heteroatom-doped graphene and combustible gas","authors":"Zhiyang Liu , Kun Chen , Rui Li, Weining Li, Minghui Gong, Xiaoqi Liu, Wei Xia, Dong Liu","doi":"10.1016/j.jaap.2024.106785","DOIUrl":"10.1016/j.jaap.2024.106785","url":null,"abstract":"<div><div>The mass production of food waste (FW) has a terrible impact on the environment, but with proper treatment, FW can be transformed into a new resource. Currently, thermal conversion (especially incineration) has been the most common and efficient means of handling FW, but it also entails negative impacts, such as high carbon emissions and lower added value. In this study, a new high-efficiency thermal conversion process is proposed that uses carbon foams to induce the formation of microwave plasma (MP), which generates very high final temperatures to enable the direct conversion of FW into combustible gases and high-value-added heteroatom-doped microwave plasma graphene (HMPG) in 5–20 s. This work investigated the optimal carbonization temperature of the melamine sponge (carbon foam precursor) and the effect of microwave plasma reaction duration on the distribution of the gas products and the properties of HMPG, and HMPG was characterized in detail by Raman spectroscopy, X-ray diffraction, scanning electron microscope, etc. Ultimately, HMPG was tested in potassium ion battery anodes for evaluation of its energy storage potential, and the results showed that the capacities were able to reach ∼270 mAh g<sup>−1</sup> at 50 mA g<sup>−1</sup> after 60 cycles.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"183 ","pages":"Article 106785"},"PeriodicalIF":5.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142327173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0