JOURNAL OF CATALYSIS
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2025
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IF 6.5
Qiangqiang Lu,Yong Kou,Lei Xiao,Jiahao Yu,Chong Chen,Jun Di,Guigao Liu,Wei Jiang,Gazi Hao
The energetic ammonium salts represent a class of oxidizer materials that are extensively utilized in contemporary propellant systems. However, the catalytic pyrolysis mechanisms of these salts remain inadequately explored, hindering the efficient application of new energetic ammonium salts. In this study, taking typical energetic ammonium salts (ammonium perchlorate (AP), ammonium nitrate (AN) and ammonium dinitramide (ADN)) as examples, their pyrolysis on the surface of the prepared Fe single-atom catalysts and the combustion flames of the powders were investigated. We learned that Fe single-atoms can promote the pyrolysis and enhance the flame intensity of ammonium salts. The mechanism of Fe single-atom catalyzed ammonium salts has been investigated through density-functional-theory (DFT) calculations, and the results well explained the experimental phenomena. The AP molecule produces oxygen most readily, primarily through the pyrolysis of *ClO 4 (−3.70 eV). The idea of solving the heat-absorbing decomposition of AN is proposed to catalyze its complete decomposition and to avoid the production of NO. The low decomposition temperature of ADN is due to the five major pyrolysis pathways of the molecule and the presence of self-catalytic intermediates. This paper offers guidelines for comprehending the pyrolysis and combustion mechanisms of energetic ammonium salts.
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高影响因子
JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2025
·
IF 6.2
Chi Li,Ji-Xiang Guo,Li Wang,Jun-Jie Luo,Qi-Ming Huang,Wen-Long Zhang,Peng-Cheng Xue
In-situ catalytic technology for heavy oil reservoirs has attracted much attention in recent years and shows great potential for efficient exploitation. However, the existing catalysts still have deficiencies in catalytic activity, stability and dispersion in the formation, which restricts their large-scale application. This study introduces a Fe-based MOF modified by oleic acid (OA), which was controllably synthesized into a highly efficient and stable hydrophobic/oleophilic Fe/MOF-OA catalyst. Under the relatively low original formation temperature of 140℃, the viscosity reduction rate of heavy oil can reach 86.5% by using 0.5 wt% catalyst and 1 wt% hydrogen donor, and the asphaltene content can be reduced by 13.82%. Comparing the experiments with and without stirring, results show that the MOF catalyst modified by OA can be better dispersed in heavy oil and achieve stable migration under reservoir conditions. The water contact angle and stability analysis tests confirm the good hydrophobic/oleophilic properties and stability of the OA-modified catalyst. Mechanism analysis shows that after modification by OA, the long-chain alkanes significantly enhance the hydrophobic/oleophilic property of the catalyst, allowing it to fully contact with heavy oil and maximize the catalytic performance of the catalyst. More importantly, this oleophilic catalyst can achieve effective migration and distribution under the spontaneous disturbances in the oil reservoir, avoiding the agglomeration and deactivation of traditional catalysts due to their inability to disperse under formation conditions. Secondly, the grafting of OA long chains can fine-tune the electronic environment of the Fe metal active center, enhance their ability to accept the lone pairs of electrons from heteroatoms in heavy oil components, promote the occurrence of deheteroatomization reactions, and lead to the cleavage of C-S, C-N, and C-O chemical bonds. In addition, compared with traditional in-situ thermal cracking catalysts for heavy oil, Fe/MOF-OA has more outstanding performance in use and economic advantages. This study provides an important theoretical basis and practical strategies for the design of in-situ catalysts for heavy oil. It demonstrates the great application potential of oleophilic MOF in the pyrolysis and upgrading heavy oil.
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COMBUSTION AND FLAME
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2025
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IF 6.2
Zhongkai Liu,Mengqi Wu,Zhaohan Chu,Xiaoqing Wu,Jiabin Huang,Jiuzhong Yang,Bin Yang,Feng Zhang
In this work, we conducted a combined experimental and theoretical investigation into the reactivity of naphthylmethyl radical (1-A2CH 2 , C 11 H 9 ) with allene (aC 3 H 4 ) and propyne (pC 3 H 4 ). Co-pyrolysis experiments of 1-(chloromethyl)naphthalene (1-A2CH 2 Cl) with aC 3 H 4 or pC 3 H 4 were studied using a flash pyrolysis microreactor coupled with synchrotron vacuum ultraviolet photoionization mass spectrometry. Significant signals at m/z = 39 (C 3 H 3 ), attributed to the rapid H-abstraction and/or pyrolysis of C 3 H 4 molecules, were detected in both experiments, indicating concurrent radical-radical (1-A2CH 2 + C 3 H 3 ) and radical-molecule (1-A2CH 2 + aC 3 H 4 /pC 3 H 4 ) reactions. Theoretical calculations reveal that the radical-radical reaction is kinetically favored under experimental conditions compared to the radical-molecule reaction, dominantly forming two C 14 H 12 adducts, 1-(1,2-butadiene-4-yl)naphthalene (1-W1) and 1-(but‑yn-3-yl)naphthalene (1-W2), along with minor amounts of other C 14 H 12 isomers and C 14 H 11 + H products. The computed rate coefficients and branching ratios of various reaction channels expand the analysis to broader temperature and pressure ranges. The radical-radical products (1-W1 and 1-W2) dominate at atmospheric-to-high pressures (>1 atm) or relatively lower temperatures (<1500 K). At higher temperatures and low pressures, competition arises between radical-radical and radical-molecule pathways. Furthermore, the structures of bimolecular products differ significantly between the 1-A2CH 2 + aC 3 H 4 and 1-A2CH 2 + pC 3 H 4 reaction systems, with implications for the formation of larger polycyclic aromatic hydrocarbons.
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JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2025
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IF 6.2
Shan Cao,Zhiqiang Chen,Ziyue Tang,Yingquan Chen,Mingwei Xia,Haiping Yang,Wei Chen,Xu Chen,Hanping Chen
Potassium-assisted biomass pyrolysis is highly efficient for product poly-generation and upgrading. In this study, kinetics modeling of over-saturated potassium (K 2 CO 3 )-assisted lignocellulose pyrolysis process was carried out by using the modified Friedman-based master plot (MF-MP) method combined with multiple-parallel compensation-simplified distributed activation energy model (CS-DAEM). The effects of K 2 CO 3 dosage on the lignocellulose pyrolysis process were also studied. MF-MP results show that all the K 2 CO 3 -assisted pyrolysis processes of cellulose, xylan, and lignin obey the Avrami-Erofeev (Am) nucleation mechanism, where potassium slightly decreases the activation energies. The potassium-assisted pyrolysis process of typical lignocellulose (bamboo) also obeys the Am mechanism, and 3G-Am-CS-DAEM modeling of the processes achieves R 2 > 0.999. By fixing the pre-exponential factor, the compensation effect was simplified. Based on modeling results, the activation energy decreases as potassium dosage increases from 0.01 mmol/g to 10 mmol/g. This study provides an effective kinetics approach to characterize the potassium-assisted biomass pyrolysis process.
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ChemistrySelect
·
2024
·Vol. 9
·期 38
·e202402768
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IF 1.9
Guangfei Qu,Yun Zhang,Junyan Li,Zhishuncheng Li
Graphical Electrochemically catalyzed ionic liquid technology facilitates lignin cleavage at 230 °C, with vanillin yields reaching 88.54 % at 3 V and guaiacol yields at 48.24 % at 4 V, showcasing enhanced productivity in lignin-derived compounds. Significant attention has been devoted to using biomass as a renewable resource to address the energy crisis and mitigate environmental pollution. Biomass, a potential substitute for fossil fuels, contains a substantial amount of lignin, ranging from 10 % to 25 %. Hence, it is crucial to research lignin depolymerization. In this study, the use of electrochemically catalyzed ionic liquids enabled the cracking of lignin at low temperatures. Specifically, by applying a low voltage at 230 °C, the controlled generation of vanillin and guaiacol was achieved. The concentration of vanillin in the depolymerized lignin reached 88.54 % under 3 V conditions. Similarly, it is presumed that the yield of guaiacol at 4 V is 48.24 %. These findings have significant implications for the targeted management of lignin depolymerization byproducts. Ultimately, this project establishes a framework for the high-value utilization of biomass and provides new perspectives on addressing the energy problem and environmental degradation.
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FUEL
·
2021
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IF 6.609
Zhipeng Tian,Xuebin Liang,Rongxuan Li,Chao Wang,Jianping Liu,Libin Lei,Riyang Shu,Ying Chen
Catalytic hydrodeoxygenation (HDO) is a popular route to upgrade the pyrolysis lignin-oil that is abundant of phenolic compounds, and the synergistic effect of bimetal enables to improve the catalytic activity significantly. In this work, a series of non-noble metal catalysts are synthesized and their HDO performances of guaiacol are compared. Optimized NiCo/SiO 2 -ZrO 2 catalyst expresses a 100% conversion and a 99.9% selectivity of cyclohexane product, which is higher than those over Ni/SiO 2 -ZrO 2 catalyst. Catalyst characterization results demonstrate that the interaction between Ni and Co promotes the reduction of metal site and the adsorption of hydrogen, which is the crucial factor during HDO process. Besides, the electron transfer from Co to Ni species weakens the C-O bond of substrate intermediate and results in its cleavage to transform cyclohexanol to cyclohexane. This is also the rate determining step in the HDO of guaiacol. Specific kinetic study is conducted to verify the reaction pathway and the structure–activity relationship. The HDO reaction of guaiacol on NiCo/SiO 2 -ZrO 2 fits the first order kinetic model well. The apparent E a of 55.9 kJ·mol −1 is lower than those of the noble metal catalysts reported in previous studies. In addition, the upgrading of raw pyrolysis lignin-oil on this non-noble bimetallic catalyst also achieves a high HDO efficiency, with the hydrocarbon contents increased from 4.2% to 60.6%. The good HDO performance of this cheap and easy-prepared NiCo catalyst proves its promising potential in the upgrading of lignin-oil for the production of hydrocarbon fuels.
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JOURNAL OF THE ENERGY INSTITUTE
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2026
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IF 6.5
Liqin Yang,Peng Lv,Jiaofei Wang,Xudong Song,Juntao Wei,Yonghui Bai,Weiguang Su,Guangsuo Yu
V 2 O 5 -modified hierarchical ZSM-5 catalysts were synthesized. • The catalysts enhanced deoxygenation during biomass pyrolysis. • The obtained bio-oil was enriched in aromatic hydrocarbons. • The bio-oil upgrading mechanism over the catalysts was elucidated. Biomass catalytic pyrolysis is a key technology for converting biomass into high-value bio-oil as a sustainable alternative to fossil resources. To address the limitations of conventional microporous zeolites, such as mass transfer constraints and insufficient deoxygenation capability during bio-oil upgrading, this study employed V 2 O 5 -modified hierarchical ZSM-5 zeolite as the catalyst and corn stover as the feedstock to investigate the catalytic upgrading process. A hierarchical ZSM-5 zeolite with intercrystalline mesopores was first prepared via a mechanical ball milling-recrystallization method, followed by V 2 O 5 loading using wet impregnation. The catalyst's structure and properties were systematically characterized. Fast catalytic pyrolysis experiments of corn stover showed that the Me 0.004 support possesses a well-defined hierarchical pore structure, which facilitates the diffusion and reaction of large molecules in bio-oil. The redox properties of V 2 O 5 promoted the catalytic deoxygenation of biomass macromolecules, yielding smaller molecular intermediates. These intermediates subsequently underwent a series of reactions, including Diels–Alder cyclization and dehydrogenative aromatization, leading to the formation of aromatic hydrocarbons (AHs) over the ZSM-5 catalyst. In particular, the V2/Me 0.004 catalyst achieved an aromatic hydrocarbon yield 1.94 times higher than that of conventional ZSM-5. Based on pyrolysis experiments with model compounds, possible reaction pathways for AHs formation from corn stover over the developed catalyst were proposed. This study provides a theoretical foundation and technical support for the production of high-value chemicals, contributing to the advancement of efficient biomass resource utilization. Download: Download high-res image (540KB) Download: Download full-size image
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ACS Applied Energy Materials
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2021
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IF 6.024
Qiang Chang,Liu Yao,Wenping Zha,Meifen Wu,Fangfang Xu,Zhaoyin Wen
Silicon is an attractive anode material for the high-energy-density lithium-ion battery due to its high theoretical capacity (4200 mA h g–1). However, larger volume expansion (∼300%) and pulverization during cycling hinder the commercialization of silicon anodes. The modification of silicon materials is a widely recognized approach to enhance the anode performance, but the volume expansion cannot be solved completely when only focusing on the active material but ignoring the overall structural optimization of the anode. In the study, additional hierarchical pores were constructed in the electrodes by in situ partial pyrolysis of the binder sodium carboxymethyl cellulose (CMC) at low temperature. Benefiting from the extra buffer space, the electrodes can accommodate more expansion and enhance the conduction of electrons and ions. In addition, the partially degraded CMC reduced the adsorption energy between the binder and the active material, reducing the stress during the swelling process, which is demonstrated by density functional theory. The as-obtained electrode delivered a high reversible capacity of 1035 mA h g–1 at 1000 mA g–1, while the capacity retention was 78.7%, and the Coulombic efficiency was stable at 99.3% after 200 cycles. The modification of the electrode structure provides guidance for the construction of high-efficiency anodes.
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JOURNAL OF THE ENERGY INSTITUTE
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2019
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IF 3.774
Xiaohua Li,Wenbin Dong,Jin Zhang,Shanshan Shao,Yixi Cai
The Fe-, Co-, Cu-loaded HZSM-5 zeolites were prepared via impregnation method. The upgrading by catalyst on biomass pyrolysis vapors was conducted over modified zeolites to investigate their catalytic upgrading performance and anti-coking performance. The Brønsted acid sites amount on Cu-,Co-loaded HZSM-5 decreased sharply, while that of Lewis both increased. The yield of liquid fraction and refined bio-oil over metal loaded ZSM-5 catalysts decreased, while that of char almost kept constant. The physical property of refined bio-oil was promoted in terms of pH value, dynamic viscosity and higher heating value (HHV). FT-IR analysis revealed that the chemical structure of refined bio-oil obtained over Fe-, Co-, Cu-loaded HZSM-5 zeolites was highly similar. The yield of monocyclic aromatic and aliphatic hydrocarbon over Fe-,Co-loaded HZSM-5 were boosted by around 2.5 times compared with original ZSM-5 zeolites. Data analysis revealed that Cu/HZSM-5 presented the worst deoxygenation ability. The anti-coking capability of Fe/HZSM-5 was obviously better, i.e., the coke content showed an approximate decrease of 38%. Thus, this study provided an efficient Fe/HZSM-5 catalysts for preparation of bio-oil derived from catalytic upgrading of biomass pyrolysis vapor.
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JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS
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2016
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IF 3.652
Bo Zhang,Guiwei Tan,Zhaoping Zhong,Roger Ruan
In order to minimize coke yield and improve hydrocarbon production during microwave-assisted catalytic fast pyrolysis of spent edible mushroom substrate, ZSM-5 zeolite catalyst is modified with pre-coking treatment, chemical vapor deposition of SiO 2 , and ethylene diamine tetraacetie acid (EDTA) chemical modification method, respectively (labeled PC-ZSM-5, SiO 2 -ZSM-5 and EDTA-ZSM-5). Experimental results show that all the modification methods result in a loss of external acid sites of ZSM-5. Among the three modified catalysts, the maximum oil fraction yield and the minimum coke yield are obtained with SiO 2 -ZSM-5. The relative content of hydrocarbons in oil fraction increases in the following order: SiO 2 -ZSM-5 > EDTA-ZSM-5 > PC-ZSM-5 > original ZSM-5. Moreover, SiO 2 -ZSM-5 shows the highest relative contents of toluene and xylene, whereas original ZSM-5 produces the lowest ones. Besides, the selectivity of benzene in aromatics follows the order of original ZSM-5 > EDTA-ZSM-5 > PC-ZSM-5 > SiO 2 -ZSM-5, while the selectivity of toluene + xylene presents the opposite trend.
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高影响因子
BIORESOURCE TECHNOLOGY
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2014
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IF 5.039
Xinhua Shi,Jie Wang
The pyrolysis characteristics of xylan , cellulose, ADF (a mixture of cellulose and lignin extracted from pine wood) and pine wood were investigated in a fixed-bed reactor by determining the distributions of three-phase products, the elemental compositions of char products, the conversions of components and the profiles of gas release rate during pyrolysis as well as the compositions of liquid products. Interactions were found to occur between the different components. Lignin accelerated the release of CO 2 and CO from cellulose and intensified the decomposition of cellulose to smaller molecular weight liquid compounds. Pine wood exhibited the componential interactions, resulting in the broadened temperature range of mass loss, the enhanced yield of char, and the increased heterogeneity of char. Pine wood produced more bio-oil than each component sample, with the compositional formula of CH 1.07 O 0.31 . The formation of liquid compounds from pine wood was also observed to be influenced by the componential interactions.
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高影响因子
PROCEEDINGS OF THE COMBUSTION INSTITUTE
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2022
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IF 6.535
Wen-luan Xie,Bin Hu,Ying Liu,Hao Fu,Ji Liu,Bing Zhang,Qiang Lu
Lignin pyrolysis involves complex radical reactions, whereas the radical chain process, especially the influence of aliphatic substituents , has been rarely studied. Herein, the typical β -O-4 lignin dimer, phenethyl phenyl ether (PPE), and three aliphatic substituted derivatives of PPE, namely α -OH substituted, β -CH 2 OH substituted, and α,β -disubstituted PPE ( α PPE, β PPE, and αβ PPE) were employed as model compounds. DFT calculations, electronic analyses, and fast pyrolysis experiments were combined to investigate three core steps of the radical chain mechanism in lignin pyrolysis, i.e., homolysis, hydrogen abstraction , and radical decomposition. The pathway involving successive C β -O homolysis → α -hydrogen abstraction → C β -O breakage of α -dehydrogenated radical is dominated for the pyrolysis of aliphatic substituted β -O-4 linked lignin, with the formation of phenolics . The hydrogen abstraction reactions at the C α site are obviously superior to those at other sites for PPE derivatives, due to the p- π conjugate stability. Notably, α -hydrogen abstraction can be significantly promoted by the π -electron-dispersing α -OH substitution. The decomposition step of dehydrogenated radicals can be facilitated by the electron-donating β -CH 2 OH substitution, where the C β -O breakage of the α -dehydrogenated radical is dominant. Totally, aliphatic substituents can improve the radical growth stage and change the competitiveness of the hydrogen abstraction and radical decomposition reactions. The fast pyrolysis experiments of PPE and α PPE gave direct proof that the generation of characteristic products from the radical chain process, i.e., benzaldehyde and phenylacetaldehyde, was enhanced by the α -OH substitution. The present work offers the potential to give a comprehensive image of the radical chain mechanism in lignin pyrolysis.
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