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Thermochemical Aspects of Activated Ammonium Perchlorates with Superior Thermal Stability,Decomposition Enthalpy,Propagation Index,and Decomposition kinetic parameters

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Journal of Thermal Science 2021年第6期30卷 2196-2201页

作者： SHERIF Elbasuney M.Yehia SHUKRI Ismael SHERIF Farag AHMED Saleh GHARIEB S.El-Sayyad Head of Nanotechnology Research Center Military Technical College(MTC)Cairo 11646Egypt School of Chemical Engineering Military Technical College(MTC)Cairo 11646Egypt Science and Technology Center of Excellence Cairo 11646Egypt Drug Radiation Research Department National Center for Radiation Research and Technology(NCRRT)Egyptian Atomic Energy Authority(EAEA)Cairo 11646Egypt

Ammonium perchlorate(AP)includes oxidizing and reducing elements on the same molecule.AP can act as an efficient oxidizer and mono-propellant as well.In this study,AP experienced crystallographic phase change from orthorhombic centrosymmetric to non-centrosymmetric under controlled isothermal heat treatment.XRD diffractograms confirmed this crystallographic phase change.The thermal behaviour of activated AP had been investigated using DSC.Activated AP demonstrated high chemical stability with an increase in endothermic phase transition enthalpy by 170%.The enthalpy of the subsequent two main exothermic decomposition reactions was increased by 250%.Whereas AP demonstrated total decomposition enthalpy of 733 J/g,activated AP showed 2614 J/g.Activated AP can secure self-sustained response at a high rate.Propagation index(combustion enthalpy/ignition temperature)was employed to assess self-sustained reaction propagation.Activated AP demonstrated high propagation index of 8.7 compared with 2.5 for un-activated AP.Primary decomposition kinetic parameters had investigated using Kissinger and KAS methods.Activated AP showed an increase in activation energy by 89%using the Kissinger method;kinetic parameters using the KAS method were in good agreement with the Kissinger method.It can have concluded that AP with novel kinetic decomposition parameters for enhanced safety storage and high combustion characteristics has evolved.

关键词： solid propellants oxidizers thermal behavior kinetic parameters activation energy

Multi-time scale identification of key kinetic processes for lithium-ion batteries considering variable characteristic frequency

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Journal of Energy Chemistry 2023年第7期82卷 521-536,I0011页

作者： Haotian Shi Shunli Wang Jianhong Liang Paul Takyi-Aninakwa Xiao Yang Carlos Fernandez Liping Wang School of Information Engineering Southwest University of Science and TechnologyMianyang 621010SichuanChina Department of Mechanical Engineering Tsinghua UniversityBeijing 100084China School of Pharmacy and Life Sciences Robert Gordon UniversityAberdeen AB10-7GJUK

The electrification of vehicles puts forward higher requirements for the power management efficiency of integrated battery management systems as the primary or sole energy supply.In this paper,an efficient adaptive multi-time scale identification strategy is proposed to achieve high-fidelity modeling of complex kinetic processes inside the battery.More specifically,a second-order equivalent circuit model network considering variable characteristic frequency is constructed based on the high-frequency,medium-high-frequency,and low-frequency characteristics of the key kinetic processes.Then,two coupled sub-filters are developed based on forgetting factor recursive least squares and extended Kalman filtering methods and decoupled by the corresponding time-scale information.The coupled iterative calculation of the two sub-filter modules at different time scales is realized by the voltage response of the kinetic diffusion process.In addition,the driver of the low-frequency subalgorithm with the state of charge variation amount as the kernel is designed to realize the adaptive identification of the kinetic diffusion process parameters.Finally,the concept of dynamical parameter entropy is introduced and advocated to verify the physical meaning of the kinetic parameters.The experimental results under three operating conditions show that the mean absolute error and root-mean-square error metrics of the proposed strategy for voltage tracking can be limited to 13 and 16 mV,respectively.Additionally,from the entropy calculation results,the proposed method can reduce the dispersion of parameter identification results by a maximum of 40.72%and 70.05%,respectively,compared with the traditional fixed characteristic frequency algorithms.The proposed method paves the way for the subsequent development of adaptive state estimators and efficient embedded applications.

关键词： Lithium-ion battery kinetic parameters Entropy evaluation Parameter identification Frequency characteristic

Effect of acid-associated mechanical pretreatment on the hydrolysis behavior of pine sawdust in subcritical water

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Chinese Journal of Chemical Engineering 2023年第6期58卷 195-204页

作者： Wei Yang Yalun Ma Xu Zhang Fan Yang Dong Zhang Shengji Wu Huanghu Peng Zezhou Chen Lei Che College of Engineering Huzhou UniversityHuzhou 313000China School of Science and Engineering Huzhou CollegeHuzhou 313000China College of Materials and Environmental Engineering Hangzhou Dianzi UniversityHangzhou 310018China

The effects of sulfuric acid-associated mechanical pretreatment on the hydrolysis behavior of pine sawdust were investigated in this study.Sulfuric acid could act as an acidic catalyst to depolymerize holocellulose through cleavage of the glycosidic bonds,the dissociation energies of which were supplied by the impact of a ball on pine sawdust,during milling.The destruction of glycosidic and hydrogen bonds in pine sawdust resulted in a decrease of crystallinity and an increase of water solubility.The sulfuric acid could promote the hydrolysis of holocellulose and its hydrolysis products.It also destroyed the chemical linkages between holocellulose and lignin during ball milling.The cleavage of chemical linkages with holocellulose made lignin more difficult to hydrolyze in subcritical water,and higher activation energy was needed to hydrolyze pretreated pine sawdust at higher reaction temperatures.It also led to the formation of glucose char and aromatic-linked polymer char from the hydrolysis products of holocellulose.

关键词： Acid-associated mechanical pretreatment Subcritical water Pine sawdust Hydrolysis behavior kinetic parameters

Conductive proteins-based extracellular electron transfer of electroactive microorganisms

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Quantitative Biology 2023年第4期11卷 405-420页

作者： Junqi Zhang Zixuan You Dingyuan Liu Rui Tang Chao Zhao Yingxiu Cao Feng Li Hao Song Frontier Science Center for Synthetic Biology(Ministry of Education) Key Laboratory of Systems Bioengineeringand School of Chemical Engineering and TechnologyTianjin UniversityTianjinChina

Electroactive microorganisms(EAMs)could utilize extracellular electron transfer(EET)pathways to exchange electrons and energy with their external surroundings.Conductive cytochrome proteins and nanowires play crucial roles in controlling electron transfer rate from cytosol to extracellular electrode.Many previous studies elucidated how the c-type cytochrome proteins and conductive nanowires are synthesized,assembled,and engineered to manipulate the EET rate,and quantified the kinetic processes of electron generation and EET.Here,we firstly overview the electron transfer pathways of EAMs and quantify the kinetic parameters that dictating intracellular electron production and EET.Secondly,we systematically review the structure,conductivity mechanisms,and engineering strategies to manipulate conductive cytochromes and nanowire in EAMs.Lastly,we outlook potential directions for future research in cytochromes and conductive nanowires for enhanced electron transfer.This article reviews the quantitative kinetics of intracellular electron production and EET,and the contribution of engineered c-type cytochromes and conductive nanowire in enhancing the EET rate,which lay the foundation for enhancing electron transfer capacity of EAMs.

关键词： c-type cytochromes conductive nanowires extracellular electron transfer kinetic parameters synthetic biology

Removal characteristics and kinetic analysis of an aerobic vapor-phase bioreactor for hydrophobic alpha-pinene

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Journal of Environmental Sciences 2012年第8期24卷 1439-1448页

作者： Yifeng Jiang Shanshan Li Zhuowei Cheng Runye Zhu Jianmeng Chen College of Biological and Environmental Engineering Zhejiang University of Technology Hangzhou 310032 China Engineering Research Center of the Ministry of Education for Bioconversion and Biopurification Zhefiang University of Technology Hangzhou 310032 China

Biofiltration is considered an effective method to control volatile organic compounds （VOCs） pollution. This study was conducted to evaluate the potential use of a bacterial biofilter packed with wood chips and peat for the removal of hydrophobic α-pinene. When inoculated with two pure degraders and adapted activated sludge, a removal efficiency （RE） of more than 95% was achieved after a start- up period of 11 days. The maximum elimination capacity （EC） of 50 g/（m^3.hr） with RE of 94% was obtained at empty bed retention time （EBRT） of 102 sec. When higher α-pinene concentrations and shorter EBRTs were applied, the REs and ECs decreased significantly due to mass-transfer and biological reaction limitations. As deduced from the experimental results, approximately 74% of ct-pinene were completely mineralized by the consortiums and the biomass yield was 0.60 g biomass/g α-pinene. Sequence analysis of the selected bands excised from denaturing gradient gel electrophoresis revealed that the inoculated pure cultures could be present during the whole operation, and others were closely related to bacteria being able to degrade hydrocarbons. The kinetic results demonstrated that the whole biofiltration for α-pinene was diffusion-limit controlled owing to its hydrophobic characteristics. These findings indicated that this bacterial biofiltration is a promising technology for the remediation of hydrophobic industrial waste gases containing ct-pinene.

关键词： biofilters gaseous α-pinene removal characteristics microbial community kinetic parameters

Anaerobic co-digestion of municipal biomass wastes and waste activated sludge: Dynamic model and material balances

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Journal of Environmental Sciences 2013年第10期25卷 2112-2122页

作者： Yifei Sun Dian Wang Wei Qiao Wei Wang Tianle Zhu School of Chemistry and Environment Beihang University College of Chemical Science and Engineering China University of Petroleum School of Environment Tsinghua University

The organic matter degradation process during anaerobic co-digestion of municipal biomass waste （MBW） and waste-activated sludge （WAS） under different organic loading rates （OLRs） was investigated in bench-scale and pilot-scale semi-continuous stirred tank reactors. To better understand the degradation process of MBW and WAS co-digestion and provide theoretical guidance for engineering application, anaerobic digestion model No. 1 was revised for the co-digestion of MBW and WAS. The results showed that the degradation of organic matter could be characterized into three different fractions, including readily hydrolyzable organics, easily degradable particulate organics, and recalcitrant particle organics. Hydrolysis was the rate-limiting step under lower OLRs, and methanogenesisis was the rate-limiting step for an OLR of 8.0 kg volatile solid （VS）/（m^3·day）. The hydrolytic parameters of carbohydrate, protein, and lipids were 0.104, 0.083, and 0.084 kg chemical oxygen demand （COD）/（kg COD·hr）, respectively, and the reaction rate parameters of lipid fermentation were 1 and 1.25 kg COD/（kg COD.hr） for OLRs of 4.0 and 6.0 kg VS/（m^3·day）. A revised model was used to simulate methane yield, and the results fit well with the experimental data. Material balance data were acquired based on the revised model, which showed that 58.50% of total COD was converted to methane.

关键词： anaerobic digestion material balances kinetic parameters modelling municipal biomass waste

A new kinetic model for direct CO2 hydrogenation to higher hydrocarbons on a precipitated iron catalyst:Effect of catalyst particle size

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Journal of Energy Chemistry 2017年第3期26卷 359-367页

作者： Ali Nakhaei Pour Mohammad Reza Housaindokht Department of Chemistry Faculty of ScienceFerdowsi University of MashhadP.O.Box:***MashhadIran

The kinetic of the direct COhydrogenation to higher hydrocarbons via Fischer–Tropsch synthesis（FTS）and reverse water-gas shift reaction（RWGS） mechanisms over a series of precipitated Fe/Cu/K catalysts with various particle sizes was studied in a well mixed, continuous spinning basket reactor. The iron catalysts promoted with copper and potassium were prepared via precipitation technique in various alcohol/water mixtures to achieve a series of catalyst particle sizes between 38 and 14 nm. A new kinetic model for direct COhydrogenation was developed with combination of kinetic model for FTS reaction and RWGS equilibrium condition. For estimate of structure sensitivity of indirect COhydrogenation to higher hydrocarbons, the kinetic parameters of developed model are evaluated for a series of iron catalysts with various particle sizes. For kinetic study a wide range of syngas conversions have been obtained by varying experimental conditions. The results show that the new developed model fits favorably with experimental data. The values of activation energies for indirect COhydrogenation reaction are fall within the narrow range of 23–16 kJ/mol.

关键词： Fischer–Tropsch synthesis Carbon dioxide hydrogenation Iron-based catalyst kinetic parameters

kinetics process of Tb(Ⅲ)/Tb couple at liquid Zn electrode and thermodynamic properties of Tb-Zn alloys formation

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Science China Chemistry 2017年第6期60卷 813-821页

作者： LiXia Luo YaLan Liu Ning Liu Kui Liu JinWen Pang LiYong Yuan ZhiFang Chai WeiQun Shi Laboratory of Nuclear Energy Chemistry Institute of High Energy Physics Chinese Academy of Sciences Key Laboratory of Radiation Physics and Technology Ministry of Education Institute of Nuclear Science and Technology Sichuan University

Electrochemical properties of rare-earth elements in the LiCl-KCl eutectic are important for the pyrometallurgical recycling process of spent nuclear fuels. In this work, the electrochemical properties of Tb(Ⅲ)/Tb(0) couple were studied by the cyclic voltammetry(CV) at a liquid Zn pool electrode. The results showed that this electrochemical reaction is quasi-reversible with mixed reversible diffusion control and the charge transfer control. The diffusion coefficient of Tb(Ⅲ) was determined to be in the order of ~10.5 cm2 s.1. Moreover, kinetic parameters, such as the standard rate constants(ks) and charge transfer coefficient(α) for the electroreduction of Tb(Ⅲ) to Tb(0) at the liquid Zn electrode, were calculated by the Nicholson method at 873 K. Additionally, it was found that Tb-Zn intermetallic compounds were easily to be formed in the measurements. Hence, the reduction process of Tb(Ⅲ)/Tb(0) couple on the Zn-coated Mo electrode was also studied to obtain more information of the Tb-Zn intermetallic compounds. Electrochemical signals stemming from various intermetallic compounds associated with TbZn12, Tb2Zn17, Tb13Zn58, Tb3Zn11, TbZn3, TbZn2 and TbZn, were observed. The thermodynamic data were thereafter estimated by applying the emf method at 823–923 K. The standard formation Gibbs energies and the standard equilibrium constant of each Tb-Zn intermetallic compounds were also calculated. Finally, enthalpies and entropies of formation and the apparent standard potentials of various Tb-Zn intermetallic compounds were also obtained.

关键词： Tb liquid Zn electrode kinetic parameters thermodynamic properties molten salt

Luminescence and low temperature trap centers in mixed rare earth borate crystal

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Journal of Rare Earths 2018年第10期36卷 1024-1029页

作者： D.Joseph Danie Indra Raj Panday H.J.Kim Sunghwan Kim U.Fawad Department of Physics Kyungpook National University Department of Radiological Science Cheongju University Department of Physics Kohat University of Science and Technology

The single crystal of this compound has been grown from melt by using a conventional Czochralski technique. The temperature dependent luminescence spectra were measured using a 265 nm laser as an exciting source in the range of 10-300 K. The scintillation decay time profile was measured and found to have three components. The influence of the trap centers on the luminescence properties was studied by means of thermoluminescence（TL） glow peak analysis. Low temperature TL glow peaks were measured in the temperature range of 10-300 K at the heating rate of 0.1 K/s for X-ray irradiated sample. The TL glow peak consists of two dominant peaks at 88 and 109 K. Several glow peaks with a complex nature causes the decrease in the light yield at temperatures below 250 K, and along with long scintillation decay components were observed. The trap parameters such as activation energy（E）, frequency factor（s）and order of kinetics（b） were calculated using various standard methods such as peak shape（PS）,variable heating rate（VHR）, initial rise（IR） and computerized glow curve deconvolution（CGCD）.

关键词： Rare earth Decay time Thermoluminescence kinetic parameters