Pyrolysis mechanism of ZrC precursor and fabrication of C/C-ZrC composites by precursor infiltration and pyrolysis

C/C-ZrC composites were prepared by precursor infiltration and pyrolysis using the organic zirconium as precursor.The conversion mechanisms of the precursors such as the thermal behavior,structural evolution,phase composition,microstructure,composition of the precursors and products were analyzed by thermal gravimetric analyzer,Fourier transform infrared spectrometer,X-ray diffraction and scanning electron microscope.The results indicate that the ZrC precursor transforms to inorganic ZrO2 from room temperature to 1200 ℃,then reduces to ZrC at 1600 ℃ through the carbothermal reduction reaction.The microstructure of the C/C-ZrC composites was also investigated.The composites exhibit an interesting structure,a coating composed of ZrC ceramic covers the exterior of the composite,and the ZrC ceramic is embedded in the pores of the matrix inside the composite.

Pyrolysis Mechanisms of Quinoline and Isoquinoline with Density Functional Theory

The pyrolysis mechanisms of quinoline and isoquinoline were investigated using the density functional theory of quantum chemistry,including eight reaction paths and a common tautomeric intermediate 1-indene imine.It is concluded that the conformational tautomerism of the intermediate decides the pyrolysis products(C6H6,HC≡C—C≡N,C6H5C≡N and HC≡CH)to be the same,and also decides the total disappearance rates of the reactants to be the same,for both original reactants quinoline and isoquinoline during the pyrolysis reaction.The results indicate that the intramolecular hydrogen migration is an important reaction step,which often appears in the paths of the pyrolysis mechanism.The activation energies of the rate determining steps are obtained.The calculated results are in good agreement with the experimental results.

Offgas Analysis and Pyrolysis Mechanism of Activated Carbon from Bamboo Sawdust by Chemical Activation With KOH

Bamboo sawdust was used as the precursor for the multipurpose use of waste. Offgases released during the activation process of bamboo by KOH were investigated quantitatively and qualitatively by a gas analyzer. TG/DTG curves during the pyrolysis process with different impregnation weight ratios （KOH to bamboo） were obtained by a thermogravimetric analyzer. Pyrolysis mechanism of bamboo was proposed. The results showed that the offgases were composed of CO, NO, SO2 and hydrocarbon with the concentration of 1 372, 37, 86, 215 mg/L, respectively. Thermogravimetric analysis indicated that the pyrolytic process mainly experienced two steps. The first was the low temperature activation step （lower than 300 ℃）, which was the pre-activation and induction period. The second was the high temperature activation step（higher than 550 ℃）, which was a radial activation followed by pore production. The second process was the key to control the pore distribution of the final product.

DFT Thermodynamic Research of the Pyrolysis Mechanism of the Carbon Matrix PrecursorTol uene for Carbon Material

Based on the experiments, the standard enthalpy△H■of the possible pyrolysis reactions of the carbon matrix precursor toluene was investigated by means of DFT method UB3LYP/ 3-21G *(based on semi-empirical method UAM1 and ab initio method UHF/3-21G*). The com- putation results with UB3LYP/3-21G* coincide with the experimental values well. Then, the mechanism for all types of the pyrolysis reactions of toluene was studied by UB3LYP/3-21G * The geometries of the reactant and the product radicals were optimized, meanwhile, the standard thermodynamic parameters of the pyrolysis reaction at different temperatures (298, 773, 843, 963 and 1 073 K) were calculated. The thermodynamic computation result shows that when the pyrolysis temperature of toluene is lower than 963 K, the reaction path supported by thermody- namics is that the C-H bond of the methyl on the benzene ring breaks and bitoluene form, while the temperature increases (about 1 073 K), the thermodynamic calculation result turns to support the reaction path producing phenyl radicals and methyl radicals. This mechanism is in accord with the experiments.

Pyrolysis mechanism of glucose and mannose: The formation of 5-hydroxymethyl furfural and furfural

Fast pyrolysis of biomass will produce various furan derivatives, among which 5-hydroxymethyl furfural（5-HMF） and furfural（FF） are usually the two most important compounds derived from holocellulose. In this study, density functional theory（DFT） calculations are utilized to reveal the formation mechanisms and pathways of 5-HMF and FF from two hexose units of holocellulose, i.e., glucose and mannose. In addition, fast pyrolysis experiments of glucose and mannose are conducted to substantiate the computational results, and the orientation of 5-HMF and FF is determined by 13C-labeled glucoses. Experimental results indicate that C1 provides the aldehyde group in both 5-HMF and FF, and FF is mainly derived from C1 to C5 segment. According to the computational results, glucose and mannose have similar reaction pathways to form 5-HMF and FF with d-fructose（DF） and 3-deoxy-glucosone（3-DG） as the key intermediates. 5-HMF and FF are formed via competing pathways. The formation of 5-HMF is more competitive than that of FF, leading to higher yield of 5-HMF than FF from both hexoses. In addition, compared with glucose,mannose can form 5-HMF and FF via extra pathways because of the epimerization at C2 position. Therefore, mannose pyrolysis results in higher yields of 5-HMF and FF than glucose pyrolysis.

Theoretical Study on Vibrational Spectra, Detonation Properties and Pyrolysis Mechanism for Cyclic 2-Diazo-4,6-dinitrophenol

Based on the full optimized molecular geometrical structures at the DFT-B3LYP/6- 311＋G^＊＊ level, there exists intramolecular hydrogen bond interaction for cyclic 2-diazo- 4,6-dinitrophenol. The assigned infrared spectrum is obtained and used to compute the thermodynamic properties. The results show that there are four main characteristic regions in the calculated IR spectra of the title compound. The detonation velocities and pressures are also evaluated by using Kamlet-Jacobs equations based on the calculated density and condensed phase heat of formation. Thermal stability and the pyrolysis mechanism of 2- diazo-4,6-dinitrophenol are investigated by calculating the bond dissociation energies at the B3LYP/6-311＋G^＊＊ level.

Mechanism studies of 5-HMF pyrolysis by quantum chemistry

The pyrolysis of 5-HMF was investigated using density functional theory methods at B3LYP/6-31 G++(d, p) level. Two possible pyrolytic pathways were proposed and full optimization of the energy gradient for the structures of reactants, products, intermediates and transition states of various reactions was implemented. The standard kinetic parameters in each reaction pathway were calculated and the formation and evolution mechanism of main pyrolysis products were analyzed. Bond dissociation energies calculation results show that the bond dissociation energy of CH_3—OH of 5-HMF is the lowest and the order of all kinds of bond dissociation energy is CH_3—OH<C—H<CH_3 OH—C_(aromatic)<CHO—C_(aromatic)<C_(aromatic)—H. In pathway(1), the energy barrier of furfural is 322.8 kJ/mol, the energy barrier of 2-furfuryl alcohol is 375.4 kJ/mol; the energy barrier of furan-2,5-dicarbaldehyde is 496.1 kJ/mol; the energy barrier of 5-methyl furfural is 375.8 kJ/mol, and the energy barrier of 2-methyl furan is 375.8 kJ/mol. In pathway(2), the activation energy required for open-loop with H_2O is higher.

TG-FTIR Study on Corn Straw Pyrolysis-influence of Minerals

In order to study the effect of minerals on biomass pyrolysis, experiments on pyrolysis of corn straw with different pretreatment methods were performed by using a thermogravimetric analyzer（TGA） coupled with a Fourier transform infrared （FTIR） spectrometer. The pretreatment methods included water washing and acid washing. The experimental results show that acid washing can remove almost all K^＋ and 78% of Ca^2＋ , while water washing only removes most of K ^＋. The existence of K^＋ and Ca^2＋ obviously favors the formation of compounds containing carbonyl groups and CO2 , but it will decrease the yields of compounds containing C-O-C groups. However, the formation of H2O, CO and CH4 are slightly affected by the removal of inorganic ions. With regard to the structure of the metal ions-adsorbed cellulose characterized by IR analysis, it can be considered that there is an ＂ion force＂ between metal ions and cellulosic biomass. The results of thermal kinetic analysis show that this force can make the reaction activation energy of the biomass pyrolysis decrease. A new mechanism is proposed for explaining the effect of inorganic ions on cellulose pyrolysis.

Pyrolysis behaviour and combustion kinetics of waste printed circuit boards

The effective recycling of waste printed circuit boards(WPCBs)can conserve resources and reduce environmental pollution.This study explores the pyrolysis and combustion characteristics of WPCBs in various atmospheres through thermogravimetric and Gaussian fitting analyses.Furthermore,this study analyses the pyrolysis products and combustion processes of WPCBs through thermogravimetric and Fourier transform infrared analyses(TG-FTIR)and thermogravimetry-mass spectrometry(TG-MS).Results show that the pyrolysis and combustion processes of WPCBs do not constitute a single reaction,but rather an overlap of multiple reactions.The pyrolysis and combustion process of WPCBs is divided into multiple reactions by Gaussian peak fitting.The kinetic parameters of each reaction are obtained by the Coats-Redfern method.In an argon atmosphere,pyrolysis consists of the overlap of the preliminary pyrolysis of epoxy resin,pyrolysis of small organic molecules,and pyrolysis of brominated flame retardants.The thermal decomposition process in the O_(2) atmosphere is mainly divided into two reactions:brominated flame retardant combustion and epoxy combustion.This study provided the theoretical basis for pollution control,process optimization,and reactor design of WPCBs pyrolysis.

Development review and the prospect of oil shale in-situ catalysis conversion technology

As an unconventional resource, oil shale possesses abundant reserves and significant potential for industrial applications. The rational and efficient development of oil shale resources holds immense importance in reducing national energy demand. In-situ catalytic technology, characterized by its high efficiency, low pollution, and minimal energy consumption, represents a key direction for future oil shale development. This paper provides a comprehensive review of research progress in in-situ oil shale mining technology, oil shale pyrolysis catalysts, the pyrolysis mechanism of kerogen, and the compatibility of different heating processes and catalysts. Furthermore, the paper proposes future research directions and prospects for oil shale in-situ catalytic technology, including reservoir modification, highefficiency catalyst synthesis, injection processes, and high-efficiency heating technology. These insights serve as valuable technical references for the advancement of oil shale in-situ catalytic technology.

Effect of Exogenous Carboxyl and Hydroxyl Groups on Pyrolysis Reaction of High Molecular Weight Poly(L-Lactide)under the Catalysis of Tin

The effect of exogenous hydroxyl,carboxyl groups and/or Sn^(2+) on pyrolysis reactions of poly(L-lactide)(PLLA)was investigated by thermogravimetric analysis(TGA).The activation energy(fa)of pyrolysis reactions was estimated by the Kissinger-Akahira-Sunose method.The kinetic models were also explored by the Malek method,and the random degradation behavior was determined by comparing the plots of ln{-ln[1-(1-w)05]}versus 1/7for experimental data from TGA with model reactions.The pyrolysis reaction rate of PLLA was affected slightly by exogenous hydroxyl and carboxyl groups at lower levels of Sn with 65-70 mg·kg^(-1)but increased appreciably in the presence of extraneous Sn^(2+),-COOH/Sn^(2+),or-OH/Sn^(2+).The Ea values for the pyrolysis reactions of the PLLAs that provided lactide were different under the catalysis of Sn2+in different chemical environments because Sn^(2+) can form the new Sn-carboxylate and Sn-alkoxide with exogenous carboxyl and hydroxyl groups,which were different in steric hindrance for the formation of activated complex between Sn^(2+) and PLLA.Under the catalysis of Sn^(2+),a lactide molecule can be directly eliminated selectively at a random position of PLLA molecular chains,and the molecular chain of PLLA cannot change two PLLA fragments at the elimination site of lactide.However,it was regenerated into a new PLLA molecule with the molecular weight reduced by 144 g·mol^(-1).

New flame retardant epoxy resins based on cyclophosphazene-derived curing agents

To obtain high-efficiency flame retardancy of epoxy resins,a cyclophosphazene derivative tri-(ohenylenediamino)cyclotriphosphazene(3 ACP)was successfully synthesized and used as a curing agent for the thermosetting of an epoxy resin system.The flame retardant properties,thermal stability,and pyrolysis mechanism of the resultant thermosets were investigated in detail.The experiments indicated that the synthesized thermoset achieved a UL-94 V-0 rate under a vertical burning test as well as a limiting oxygen index(LOI)of 29.2%,which was able to reach V-0 even when a small amount of 3 ACP was incorporated.Scanning electronic microscopic observation demonstrated that the char residue of the thermosets was extremely expanded after the vertical flame test.Thermal analysis showed that the samples had a lower initial decomposition temperature when 3 ACP was introduced into the epoxy resin systems.This indicates that the carbonization ability of the thermosets was significantly improved at elevated temperatures.In addition,the incorporation of 3 ACP can effectively suppress the release of combustible gases during the pyrolysis process,and the decomposition of E-44/DDS-3 ACP curing systems also promotes the formation of polyphosphoramides charred layer in the condensed phase.The investigation on the chemical structures of both the gaseous and condensed phase pyrolysis process confirmed the flame-retardant mechanism of the 3 ACP-cured epoxy resins.Therefore,the nonflammable halogen-free epoxy resin developed in this study has potential applications in electric and electronic fields for environment protection and human health.

A theoretical investigation on the thermal decomposition of pyridine and the effect of H_(2)O on the formation of NO_(x) precursors

Pyridine is one of the main nitrogen-containing compounds in coal,and its pyrolytic mechanism to generate NO_(x)precursors(mainly NH_(3)and HCN)remains unclear.In this work,the possible pathways for the pyrolysis of pyridine to form HCN and/or NH_(3)were investigated by the density functional theory method,and the effects of H_(2)O on pyridine pyrolysis were also investigated.The results show that there are two possible reactions for the initial pyridine pyrolysis,i.e.,internal hydrogen transfer and C-H bond homolysis,and that internal hydrogen transfer is more favorable.Nine possible reaction pathways following internal hydrogen transfer are obtained and analyzed.Among these pathways,pyridine prefers to produce HCN instead of NH_(3).The existence of H_(2)O has significant effects on the decomposition of pyridine,as it participates in pyridine pyrolysis to form NH_(3)rather than HCN as the major product.