Flynn-Wall-Ozawa Research Articles

Kinetic and thermodynamic study of composite with jute fiber as reinforcement

In the present work, engineered by compression molding process via a hydraulic press, the A and B composite samples were carried out with 5% and 10% ratio respectively of Ricinodendron heudelotii oil-based alkyd resin in bio-based matrix made of unsaturated polyester using jute fibers as reinforcement material. The samples’ thermal decomposition was performed through thermogravimetry (TG) and derivative thermogravimetry (DTG) analyses. Both composite samples exhibit two stages of decomposition, where the main occurs at 200 - 550°C. Aiming to study and being able to model the thermal degradation of the elaborated composites, finding the kinetic triplets appears the best option to describe the kinetic process undergo by the composites in order to evaluate the performance application of the composites. Two non-isothermal techniques, Flynn-Wall-Ozawa (FWO) and Kissinger have been used to assess the activation energy Ea, and it is found that the apparent activation energy varies with the degree of conversion indicating that both composites decompose with a multiple step mechanism process. The appropriate reaction model for the second stage of decomposition was best suited with Johnson-Mel-Avrami (n<1) model and has been established, allowing us to model thermal degradation behavior of our elaborated composite material and set predictions. The estimated Arrhenius factor values were respectively about A and B composites, 4.12.1015 min-1 and 10.42.1015 min-1, allowing us to set the final equation characterizing the degradation process for the second and main decomposition stage. Finally, as a result of comparison between A and B composites, A appears to be the more thermally stable due to its lower values of Arrhenius pre-exponential factor over the main stage of decomposition and higher calculated the activation energy values.

Investigating the catalytic effect of nanoferrites additives on the thermal decomposition of ammonium perchlorate and burning rate modification of the composite solid propellants

The co-precipitation method was used to synthesize nanosize copper ferrite (CuF) and cobalt-copper-nickel ferrite (CoCuNiF). Physico-chemical characterization of material was done using powder X-ray diffraction, Raman, UV–Vis, and atomic force microscopy (AFM). The effect of 1 % by mass additives on the thermal decomposition and kinetics parameters of ammonium perchlorate (AP) was investigated using non-isothermal isoconversional methods such as Flynn wall Ozawa (FWO), Kissinger Akahira Sunose (KAS), and Starink. The burning rate enhancement and ignition delay study were also investigated. The catalysts can decrease the activation energy of AP by 48 % along with increasing the burning rate of the corresponding composite materials. Both the catalysts can be successfully used for enhancing the burning performance of propellants and hence can be used for rocket and missile propulsions.

AVALIAÇÃO DA DEGRADAÇÃO TÉRMICA DO CAROÇO DE ABACATE RESIDUAL PARA A PRODUÇÃO DE BIOCARVÕES

EVALUATION OF THERMAL DEGRADATION OF RESIDUAL AVOCADO SEED FOR BIOCHAR PRODUCTION. The thermal degradation kinetics of avocado seed biomass (Persea americana) was investigated at the heating rates of 5, 15, 20 and 25 ºC min-1 using thermogravimetric (TGA) and differential thermogravimetric (DTG) analysis techniques in the temperature range from ambient to 780 ºC. Chemical analysis of the avocado seed resulted in: 51.4% cellulose, 42.4% hemicellulose, 20.1% lignin, 2.1% ash, 5.6% extractives. The pyrolysis products were characterized via FTIR, SEM/EDS. The isoconversional methods of Ozawa-Flynn-Wall (OFW) and Kissinger-Akahira-Sunose (KAS) have yielded activation energy, Eα, varying from 36-323 kJ mol-1, respectively. The calorific value of biochars produced in the present study in the range of 265 to 475 ºC was 16,17 to 20,24 MJ kg-1, respectively, which are comparable to those reported values in the literature. Analyzing the DTG simultaneously with the addition of thermal energy, it can be seen that low molecular weight compounds represent the first degradation curves, followed by hemicellulose, cellulose and, lignin. The results obtained in the present work indicate that its feasible to prepare biochars with tunable properties from residual avocado seeds using a slow pyrolysis process, adding commercial value and reducing the environmental impact caused by the inadequate disposal of lignocellulosic materials.

Thermal investigation of NbSe2 nanoparticles synthesized through a temperature-dependent sonochemical method.

Due to their unique size-dependent properties, transition metal di-chalcogenide nanoparticles are trending in research for their potential to revolutionize next-generation electronics, energy storage, and catalytic processes. This study addresses the effect of temperature when synthesizing NbSe2 nanoparticles via the sonochemical method at three different temperatures, room temperature (R.T.), 70 °C, and 100 °C. Energy Dispersive X-ray Analysis (EDAX) confirmed the high purity of NbSe2, with the sample synthesized at 70 °C, displaying the accurate stoichiometric ratio. X-ray diffraction (XRD) analysis revealed that all samples maintained the hexagonal phase of NbSe2, with 70 °C exhibiting superior crystallinity due to their crystallite size, lowest dislocation density, and minimal internal strain. Thermogravimetric analysis (TGA) and differential thermogravimetric (DTG) analyses, demonstrated that the sample synthesized at 70 °C had the highest thermal stability, with the lowest total weight loss and most consistent mass loss behavior. Kinetic parameters were evaluated using the Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) methods, determining activation energy (E a), pre-exponential factor (A), change in activation enthalpy (ΔH*), change in activation entropy (ΔS*), and Gibbs free energy change (ΔG*). Also, the sample synthesized at 70 °C exhibited the highest E a, indicating superior thermal stability and favorable reaction kinetics. The findings underscore the significant impact of synthesis temperature on the structural and thermal properties of NbSe2 nanoparticles, with the sample synthesized at 70 °C demonstrating optimal characteristics. This study provides valuable insights into temperature-dependent synthesis and the thermal behavior of NbSe2 nanoparticles, highlighting their potential in various technological applications.

Pyrolysis mechanism and pyrolysis kinetics of yellow wine lees.

Yellow wine lees, a by-product produced while brewing yellow wine, can be a helpful biomass resource through pyrolysis. However, there have been very few studies on the pyrolysis of yellow wine lees. The kinetics and mechanism of pyrolysis in yellow wine lees were explored through an extensive study of their chemical and elemental composition. The pyrolysis mechanism of yellow wine lees was further studied using thermogravimetric analysis (TGA) from 30 °C to 900 °C. The TG/DTG analysis showed that yellow wine lees thermally decomposed mainly between 121 °C and 500 °C. The maximum decomposition was observed between 218 °C and 326 °C, with a clear peak at 298 °C. Upon analyzing the 3D-FTIR results, the gas phase products at this stage primarily included inorganic molecules like CO2, H2O, and CH4, along with organic compounds such as esters, alcohols, phenols, amines, ethers, aldehydes, ketones, and acids. The Maillard reaction and ketosis decarboxylation primarily occurred in proteins (amino acids) and carbohydrates. The pyrolysis kinetics of yellow wine lees were analyzed utilizing the distributed activation energy model (DAEM). The results of DAEM were simultaneously verified using the Flynn-Wall-Ozawa (FWO) method. The findings indicated that the pyrolysis of yellow wine lees conforms to the assumptions of infinite parallel reactions and activation energy distribution. As the conversion rate increased during pyrolysis, the activation energy of yellow wine lees initially increased to 210-220 kJ mol-1, then stabilized at 190-200 kJ mol-1 and rapidly decreased to approximately 100 kJ mol-1. This study offers a theoretical basis for the application of yellow wine lees using pyrolysis.

Research on the characteristics of pressured pyrolysis products of marine plastics

The problem of marine plastic pollution, mainly composed of polyolefin plastics, is becoming increasingly serious, and reducing marine plastic pollution is urgent. Pyrolysis, as a promising technology for treating polyolefin plastics such as polystyrene (PS), has great potential in addressing marine plastic pollution issues. In order to explore the possibility of resource utilization of marine plastics, this article studied the effect of pressure changes on the pyrolysis products of marine plastics. Marine PS was prepared by soaking routine PS in artificial seawater and air drying, and the most significant difference between the two was found to be the salt attached to the surface. The dynamic characteristics of marine PS were analyzed using Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods, and the apparent activation energy of marine PS calculated by FWO and KAS methods are 102.94 kJ·mol−1 and 95.76 kJ·mol−1, respectively. The effect of pressure at different temperatures on the pyrolysis products of marine PS was studied. The results indicate that the yield of pyrolysis oil decreases as the pressure is increased, while solid products are obtained from scratch. The increase in pressure will gradually make the composition of the thermolytic gas become monotonous. Under critical pressure, pressurization promotes an increase in CH4 content while reducing H2 content, causing the lower heating value of pyrolysis gas to increase to 4.355 kJ·g−1. Analysis of oil content found that increasing pressure promotes the growth of Benzene Toluene Ethylbenzene & Xylene (BTEX) to 33.61%, but excessive pressure can significantly reduce the higher heating value from 42.116 MJ·kg−1 to 31.825 MJ·kg−1. The solid products were characterized using FTIR and it was found that pressure did not have a significant impact on surface functional groups. Increasing the pressure properly promotes the agglomeration of amorphous carbon.

Co-pyrolysis of thermoplastic polyurethane with paulownia wood: Synergistic effects on product properties and kinetics

Co-pyrolysis of plastics and biomass offers an effective approach for waste disposal. In this study, the synergistic effects during the co-pyrolysis of thermoplastic polyurethane (TPU) and paulownia wood (PAW) were investigated in terms of pyrolysis kinetics and product properties using tube furnace, TG-FTIR and GC/MS. The results revealed that co-pyrolysis promoted the material pyrolysis and facilitated the pyrolysis process taking place at low temperatures. By adopting the Kissinger-Akahira-Sunose (KAS), Flynn-Wall-Ozawa (FWO) and Starink methods, the average activation energies of pure TPU, PAW, and TPU/PAW blends with a 1:1 mass ratio were determined to be 139 kJ/mol, 288 kJ/mol, and 126 kJ/mol. It is indicated that co-pyrolysis significantly reduced the activation energies and enhanced reactivity. Tube furnace experiments demonstrated that TPU/PAW blend with 1:1 mass ratio exhibited the highest synergism. The TPU melt acted as a physical barrier, leading to increased production of char and oil, and lower production of volatile gas. In the pyrolysis oil, the synergistic effect effectively hindered a formation of alcohol phenols. In the meanwhile, the synergistic effect also boosted generations of aliphatic compounds and ketones, increasing the heat value use of pyrolysis oil. Furthermore, a reaction pathway and mechanism of co-pyrolysis of TPU and PAW was proposed. The active molecules and free radicals generated by the pyrolysis of PAW promote the hydrogen transfer cyclization of polyester polyols decomposed by TPU, and the hydrogen free radicals released by TPU promote the depolymerization and activation of PAW. Moreover, the catalytic effect of alkali metal elements in PAW promotes the synergistic effect. The results of the study provide a basis for the co-pyrolysis of waste plastics and biomass to achieve high value utilization of waste.

The influence of B doping on phase formation and microstructural evolution in NHL during solid-state reactions

Natural Hydraulic Lime (NHL), was synthesized by doping B2O3 into calcium carbonate and silica aerogel. By introducing varying levels of B3+ ion doping (0/1/5/10/15/20/25 mol%), a range of NHL compositions were successfully prepared, thereby enabling regulation of the NHL phase composition. Furthermore, through the doping of 25 mol% B3+ ions, in-depth investigations employing XRD, SEM, and FT-IR were conducted to explore phase transitions and ion migration during NHL calcination at different temperatures. Thermal analysis kinetics studies further revealed the variation of activation energies for CaCO3 decomposition and C2S crystallization with changing levels of B3+ ion doping. The introduction of B ions was observed to stabilize the α’ phase of dicalcium silicate (C2S) and moderately enhance the reactivity of calcium oxide (CaO). B3+ ions significantly influenced the crystallization mechanism of C2S, shifting it from a diffusion-controlled process to a heterogeneous nucleation process. The application of the Kissinger and Flynn-Wall-Ozawa (FWO) methods assisted in elucidating the underlying reasons for these differences. Both approaches demonstrated a substantial decrease in activation energy, signifying the pronounced influence of B doping on the sintering regime and phase transition mechanism of NHL. In summary, the precise modulation of NHL phase composition and sintering regime was achieved through B doping. These findings not only deepen our understanding of the mechanistic role of B3+ ions in NHL preparation and application but also offer robust guidance for the production process of NHL.

Research on the Combustion Performance of Municipal Solid Waste in Different Sorting Scenarios: Thermokinetics Investigation via TG-DSC-FTIR-MS.

Waste sorting is regarded as one of the most important strategies for municipal solid waste (MSW) management. The changes in the combustion parameters after MSW sorting had a significant impact on the actual operation of the boiler. In the present study, the effects of heating rate on combustion characteristics and dynamics of MSW in different sorting scenarios were studied using the thermogravimetry (TG)-differential scanning calorimetry (DSC)-Fourier transform infrared (FTIR)-mass spectrometry (MS) technique. TG-DSC analysis showed that the heat released from MSW combustion at different heating rates ranged from 1394.1 to 4130.1 J/g. According to the TG-DTG curves, the combustibility of 30% sorted MSW was increased by 1.2 times compared to that of the unsorted scenario. In the 30% sorted scenario, the average activation energies were estimated to be 161.24 and 159.93 kJ/mol based on the Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) methods, respectively. Based on the Coats-Redfern (CR) method, the minimum activation energies for unsorted and 20% sorted scenarios were 148.74 and 135.53 kJ/mol at 523 to 606 K, respectively, while they were 29.42 and 33.22 kJ/mol at 606 to 780 K. XRF analysis showed that the alkali and alkaline earth metal oxides in the ash contributed to a high risk of slagging and scaling. This work can provide a scientific basis for the real situation of MSW incineration.

Thermal degradation kinetics, thermodynamics and pyrolysis behaviour of polycarbonate by TGA and Py-GC/MS

This paper elucidates the thermal and catalytic (mordenite and y-zeolite) pyrolysis characteristics of Polycarbonate (PC) as well the kinetics and thermodynamic parameters of the thermal decomposition of PC. Three distinct isoconversional methods, namely the Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Starkin methods, were employed to evaluate the kinetic and thermodynamic parameters. The average activation energies determined with the KAS, FWO, and Starink methods were 245.81, 235.36, and 249.99 kJ/mol respectively, and they were reduced by 17 % and 21 % when mordenite and y-zeolite were utilized as catalysts, respectively, according to the calculations performed with the KAS method. Py-GC/MS analyses showed that phenolic components were found to be dominant in the oil product obtained under non-catalytic conditions. Micropores in the structure of y-zeolite constitute 54.4 % of the total surface area, while micropores in the structure of mordenite constitute 95.5 % of the total surface area. Depending on the structure of the catalysts used, phenolic components decreased slightly, and aromatic and PAH (Polycyclic Aromatic Hydrocarbons) components replaced these components. As a result, phenolic compounds in the oil product obtained with y-zeolite (56.7 %) were less than those produced with mordenite (61.02 %). PAHs were 12.9 % and 7.5 % in the presence of y-zeolite and mordenite, respectively. Thus, the results evidence the molecular size of zeolite catalysts, as well as their acidic structure, which are crucial factors in the conversion of phenolic compounds.

Effect of sludge-based suppression materials on the explosive flame characteristics of aluminium dust

A study was conducted to investigate the inhibitory effect of sludge-based phosphate-containing composite powder explosion suppressants (MPP/AMS) on aluminium dust explosion and combustion. The experiment compared the inhibition characteristics of ordinary sewage sludge particles, high-temperature alkali-modified sludge particles, phosphate-containing particles, and phosphate-modified sludge particles. The study utilized a flame propagation experimental device and an explosion pressure testing device for comprehensive research. The experimental recording devices revealed that sludge-based composite powder explosion suppressants effectively inhibit aluminium powder explosion and combustion. Thermodynamic analysis of the rapid oxidation stage was performed using the Coats Redfern (C-R) method, and validation was conducted using the Flynn Wall Ozawa (FWO) and Kissinger Akahira Sunose (KAS) methods. The results theoretically explain that sludge-based composite powder explosion suppressants can effectively suppress aluminium powder explosions and exhibit a blocking effect. Surface morphology and material element characterization experiments were conducted before and after the explosion, combined with pyrolysis characteristics. The analysis demonstrated that the inhibition mechanism of sludge-based composite powder explosion suppressants on aluminium powder explosion primarily involves two aspects: physical inhibition (MPP coating inhibition, porous adsorption isolation) and chemical inhibition (decomposition heat absorption, product oxidation). The theoretical findings provide evidence of the superior inhibitory effects of sludge-based composite powder explosion suppressants, offering new insights for the resource utilization of sludge waste and the development of novel explosion suppression materials.

Original Synthesis of Ethylene‐Acrylic Acid (ester) Copolymers Derivatives from 5‐substituted Cyclooctenes with A Controllable Way Via Ring‐Opening Metathesis Polymerization

AbstractHigh‐value grades of ethylene‐acrylic acid (EAA) and ethylene‐acrylic ester copolymers have been producing produced from ethylene, acrylic acid (AA), and the alcohol derivative via radical reaction in autoclave reactor at a temperature of 150‒230 °C and pressure of 150–300 MPa. In this paper, EAA and its ester derivatives are originally created from the 5‐substituted cyclooctenes (COE) with side chains of carboxylic acid or ester derivatives by ring‐opening metathesis polymerization (ROMP) at normal temperature and pressure. Especially, the controllable insertion of side chain is effectively achieved by altering the molar ratio of COE and 5‐substituted COE. Furthermore, the polar carboxyl groups (ester groups) have a detrimental effect on the order assigns of the linear backbone and thus hindered crystallization, indicating relatively lower crystallizing and melting temperature with an increase in the content of side chain. As the amounts of polar groups raised, the stiffness of chain segments enhanced, thereby leading to an elevation in the copolymer's energy storage modulus (E') and glass transition temperature (Tg). Moreover, the Flynn‐Wall‐Ozawa (FWO) technique is employed to characterize and fit the non‐isothermal crosslinking kinetics of the ethylene‐acrylic ester derivatives, and the crosslinking activation energy is determined to lie between 97 and 140 kJ mol−1.

Application of used engine oil as a hydrogen-rich substance in co-pyrolysis with pine wood for reduction its environmental hazards and produced diesel-like fuel: Thermal behavior, kinetic and thermodynamic analysis

This study introduced co-pyrolysis process as effective way for convert used engine oil (UEO) into useful product and reduced its environmentally hazardous. The co-pyrolysis of acid-washed pine wood (APW) and used engine oil was investigated through thermogravimetric analysis (TGA) within the temperature range of 30 to 700 °C, employing heating rates of 5, 10, and 20 °C/min. Among the blends studied, a blend containing an equal ratio of two feeds exhibited the highest synergism. The study of the oil composition obtained from the co-pyrolysis of APW and UEO in the fixed-bed reactor showed that the simultaneous use of UEO as a feedstock reduced the yield of oxygenated compounds from 82.69 % to 25.06 %, while significantly increasing the yield of hydrocarbons from 17.31 % to 74.93 % compared to APW alone. 51.25 % of these hydrocarbons were in the range of diesel fuel. The kinetic parameters were determined using three iso-conversional methods: Kissinger-Akahira-Sunose (KAS), Ozawa-Flynn-Wall (OFW), and Starink. The obtained average activation energy was 162.65, 161.39, and 161.66 kJ/mol for FWO, KAS, and Starink, respectively. The pre-exponential factors, determined by the Kissinger method, varied from 1.98 × 108 to 9.12 × 1018. Also, the use of master plots in combination with iso-conversional methods showed that the reaction order model, f(α)= (1-α)n, with n between 2 and 3, provides the best description for the co-pyrolysis of APW and UEO in the applied heating rate range. Furthermore, with increasing conversion from 0.2 to 0.8, the thermodynamic parameters including ΔH, ΔG, and ΔS, changed in the range of 125.09–234.59 KJ/mol, 159.02–155.92 KJ/mol, and −0.06 to 0.13 KJ/mol, respectively.

The utilisation of thermally treated poultry farm waste for energy recovery and soil application

The thermal treatment was analysed of poultry farm waste, excrement and litter, and their mixture. Two thermal treatment methods were chosen: Torrefaction at 300 °C and hydrothermal carbonisation (HTC) at 250 °C. The characterisation of raw materials and solid products was performed by proximate and ultimate analysis, and analysis of the high heating value. Thermogravimetric analysis (TGA) was performed of the combustion of raw materials and solid products in an air atmosphere. The kinetic and thermodynamic parameters were determined according to the Flynn–Wall–Ozawa (FWO) kinetic model. The contents of total organic carbon, chemical oxygen demand, total nitrogen and total phosphorus, as well as the content of total phenols, were determined in the process fluids. In addition, a germination test was performed with garden cress.The results show that the torrefied biomass had a higher carbon (C) content and a higher calorific value than raw biomass. The FWO kinetic model proved to be suitable for describing the kinetic of combustion of the tested samples' high fitting coefficients. The Eα for torrefied litter, excrement and their mixture ranged between 129 and 338, 108–550 and 136–489 kJ/mol, while for the HTC-treated samples generally lower Eα values were measured, 187–364, 121–229 and 126–428 kJ/mol, respectively. Germination tests with garden cress and analysis of nutrients showed that the tested products of torrefaction and HTC have a perspective for agricultural use at a sample concentration of up to 10 wt% in the substrate.

Pyrolysis of combustible fractions in excavated waste: Effect of landfill time on pyrolysis characteristics analyzed by TG-FTIR-MS

Excavated waste in landfills contains non-negligible amounts of combustible fractions, whose mining and thermochemical treatment are promising to save land occupation and achieve energy utilization. Considering the possible changes of combustible fractions in the excavated waste during landfill time, this study comprehensively analyzed the impact of landfill time on the thermogravity characteristics, pyrolysis kinetics, products composition, and pyrolysis pathways of excavated waste using TG-FTIR-MS. The findings indicated a positive correlation between landfill time and the remaining mass resulting from pyrolysis. The activation energies for pyrolysis of excavated waste were found to be greater than those of fresh waste. Specifically, the activation energy values increased from 230.49 kJ/mol to 289.11 kJ/mol for polyethylene, from 216.38 kJ/mol to 260.91 kJ/mol for polypropylene, from 219.04 kJ/mol to 240.06 kJ/mol for expanded polystyrene, and from 210.01 kJ/mol to 279.93 kJ/mol for polyethylene terephthalate, respectively. The increment of activation energies indicates an elevated level of difficulty in the pyrolysis reaction. The pyrolysis kinetics of excavated waste were examined by the Kissinger-Akahira-Sunose (KAS), Flynn-Wall-Ozawa (FWO), and Starink methods. It was found that FWO method showed an optimal fitting result (R2 =0.9681–0.9819), while KAS and Starink methods also showed satisfactory fitting performance. The TG-FTIR-MS results revealed that the effect of landfill time on products categories are negligible, but the change in the content of pyrolysis products is more pronounced. This study is hoped to provide fundamental insights into the thermochemical disposal and energy recovery of excavated waste in landfills.

The thermal behavior during the co-combustion of bituminous coal and oil palm trunk hydrochars

ABSTRACT Utilizing oil palm trunk (OPT) residue as a co-fuel in coal-fired plants offers an environmentally favorable solution to agricultural waste disposal and fossil fuel combustion impacts. This study investigates the potential of hydrochar from OPT (HTC-OPT) as a coal-like solid fuel for co-combustion. The combustion characteristics of coal, HTC-OPT, and their blends (10–50% HTC-OPT) were analyzed via thermogravimetric analysis with heating rates ranging from 10 to 30°C/min. The Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS) models were employed to explore co-combustion interactions and kinetic parameters. Results reveal enhanced combustion efficiency with HTC-OPT addition to coal. Higher HTC-OPT ratios correlate with increased maximum combustion rates, ignition and comprehensive combustibility indices, and decreased ignition and burnout temperatures. Additionally, blended fuels exhibit a proportionally synergistic co-combustion interaction. Both KAS and FWO models indicate similar trends in activation energies, with the lowest values (49.94 kJ/mol for KAS and 60.90 kJ/mol for FWO) at a 10% HTC-OPT ratio.

Kinetics of thermal decomposition of crude oils: Insights from principal component analysis and products characterization

Energy demand is souring, and fossil fuel reserves are dwindling, making heavy oil resources more attractive. In this study, thermogravimetric and Py-GC/MS analyses were conducted on Iranian crude oil samples to compare high and low API (American Petroleum Institute) crude oils. A kinetic study based on mass loss of crude oil was performed using three model-free methods and distributed activation energy model (DAEM). To do that, TG analysis carried out, the temperature was increased from room temperature to 1000 °C with heating rates of 10, 20, and 30 °C min−1. Activation energy (Ea) and pre-exponential factor (A0) were estimated from Friedman, Kissinger–Akahira–Sunose (KAS), and Ozawa-Flynn–Wall (OFW) methods for oil sample. The Ea and A0 for heavy crude oil (Koroosh) pyrolysis varied between 59.85 and 193.83 kJ mol−1 and 1.34 × 105 to 4.36 × 1011 s−1, respectively. For light crude oil sample Lavan, the Ea and A0 ranged between 35.93 to 62.89 kJ mol−1 and 337.41–722.65 s−1, respectively. Pearson's correlation analysis found that the activation energy barrier increases as the reaction progresses and the temperature rises. This makes it harder to form the activated complex, which is a key step in the reaction. Principal component analysis supported these findings. Saturated and aromatic hydrocarbons were liberated at mild temperature while the resins and asphaltenes consecutively released in favorable condition for developing sustainable heavy oil recovery systems. Py/GC–MS analysis shows the evolution of saturated hydrocarbon in Koroosh-oil and aromatic hydrocarbons in Lavan-oil and demonstrates their suitability for fuel applications.

Construction of cobalt–nickel bimetallic coordination polymers and their catalytic thermal decomposition of ammonium perchlorate

The addition of a catalyst to ammonium perchlorate (AP) can effectively improve its thermal decomposition properties. The heterobimetallic complex Ni-Co-pzdc (2,3-pyrazinedicarboxylic acid) was synthesized via in situ substitution, and the N-doped Ni-Co-pzdc derivative was prepared by using it as a sacrificial template. A series of characterization tools were used to investigate the morphological and structural features of the resulting materials, and the thermal decomposition behaviors of the two products were investigated by homogeneous mixing with AP, respectively, and the activation energies were calculated by using Kissinger, Kissinger-Akahira-Sunose (KAS), and Flynn-Wall-Ozawa (FWO), and the results showed that both substances possessed excellent catalytic activities.

Kinetics Study on Thermal Degradation of Polystyrene and Sulfonated Polystyrene from Styrofoam Waste

This research studied kinetics of thermal degradation of polystyrene (PS), and sulfonated polustyrene (sPS) which were synthesized from styrofoam waste. The thermal study was conducted by thermogravimetric analysis (TGA) at various heating rate of 10, 15, 20 and 25 dpm. The kinetics parameters were determined by Coats Redfern (CR), Friedman (FM), Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (OFW) models. TGA result found that PS has range thermal stability of 274 – 415 oC, but sPS has range thermal stability of 175 – 582 oC. Kinetic study to PS shows that the activation energy increases by the increasing of fraction conversion for all kinetics parameters with a regression value close to 1. While in sPS, the CR method shows an increase in activation energy value with an increasing fraction convertion. On the other hand, CR-FM-KAS and OFM methods obtained an increase in activation energy, then decreased at the fraction convertion above 0.6, and received negative activation energy. The kinetics model successfully explains the degradation of PS and sPS. In addition, the high thermal stability of sPS from styrofoam waste shows that this material has good potential as polymer electrolyte materials.

Study on the combustion characteristics and kinetics of water hyacinth co-combustion with anthracite

Water hyacinth(WH) is a promising resource produced as a by-product of treating pollution in watersheds, but little study has been done on its high-value applications. In this work, the combustion characteristics of WH, anthracite (AN), and their blends under different ratios, and heating rates were investigated by the thermogravimetric (TG) analyzer. The Kissen-Akahira-Sunose (KAS) and Flynn-WallOzawa (FWO) methods are used to calculate the dynamics, and the interaction between the mixed materials is discussed. The results show that the combustion characteristics of WH are better than those of AN because of its higher volatile components. With the increase of WH, the comprehensive combustion index increased from 0.15(pure AN) to 2.22(WH: AN=5:5). With the increase in heating rate, there is no significant difference in residual. The difference in thermogravimetric curves of mixed fuel in the volatile combustion stage and fixed carbon combustion stage shows that there is an interaction between WH and AN in the process of co-combustion, indicating that the mixed fuel is suitable for co-combustion. This study provides a theoretical basis for improving the efficiency of clean energy and reducing the consumption of fossil energy.