Co-pyrolysis behaviors and kinetics of plastics–biomass blends through thermogravimetric analysis

Co-pyrolysis behaviors of plastics–biomass blends were investigated using a thermogravimetric (TG) analysis from room temperature to 873 K with a heating rate of 5–40 K min^?1 in an inert atmosphere. The selected biomass sample was sawdust of pine wood (WS). Polyvinyl chloride (PVC), low-density polyethylene (LDPE), high-density polyethylene (HDPE), and polypropylene (PP) were selected as plastic samples. The difference of mass loss between experimental and theoretical ones (calculated as arithmetic sums of those from each separated component) was used as a criterion of synergetic effect. The experimental results indicated that a significant synergetic effect existed during the high-temperature region of plastics and WS co-pyrolysis process, specially, the dehydrochlorination reaction of PVC and the degradation of hemicellulose and cellulose in the WS during the co-pyrolysis process showed synergetic effect, as well as the reaction of plastics (LDPE, HDPE, and PP) and WS. Based on the TG data with different heating rates, the kinetics parameters, especially activation energy, were calculated using the Friedman method. The activation energy of plastics, WS, and their blends were from 92.8 to 359.5 kJ mol^?1. The activation energy of the PVC–WS blends was at a range of 180.2–254.5 kJ mol^?1 in the second stages. The activation energies range of LDPE–WS, HDPE–WS, and PP–WS blends were 164.5–229.6, 213.2–234.3, and 198.4–263.6 kJ mol^?1, respectively.     

Effect of the catalyst MCM-41 on the kinetic of the thermal decomposition of poly(ethylene terephthalate)

The aim of this work is to determine the activation energy for the thermal decomposition of poly(ethylene terephthalate)—PET, in the presence of a MCM-41 mesoporous catalyst. This material was synthesized by the hydrothermal method, using cetyltrimethylammonium as template. The PET sample has been submitted to thermal degradation alone and in presence of MCM-41 catalyst at a concentration of 25% in mass (MCM-41/PET). The degradation process was evaluated by thermogravimetry, at temperature range from 350 to 500 °C, under nitrogen atmosphere, with heating rates of 5, 10 and 25 °C min^?1. From TG, the activation energy, determined using the Flynn–Wall kinetic method, decreased from 231 kJ mol^?1, for the pure polymer (PET), to 195 kJ mol^?1, in the presence of the material (MCM-41/PET), showing the catalyst efficiency for the polymer decomposition process.     

Thermal degradation kinetics study and thermal cracking of waste cooking oil for biofuel production

Thermal cracking of waste cooking oil (WCO) for production of liquid fuel has gained special interest due to the growing demand of renewable fuel, depleting fossil fuel reserves and environmental issues. In the present work, thermal cracking of WCO to produce liquid hydrocarbon fuels without any preprocessing has been studied. Moreover, non-isothermal kinetics of WCO using thermogravimetric analysis (TGA) has been studied under an inert atmosphere at various heating rates. According to TGA result, active thermal decomposition of WCO was found to be between 318 and 500 °C. Furthermore, the temperature at which the maximum mass loss rate attained was shifted to higher values as the heating rates increased from 10 to 50 °C min^?1 and the values were found to be approximately similar to that of R ₅₀. Besides, model-free iso-conversion kinetic methods such as Friedman (FM), Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) were used to determine the activation energies of WCO degradation. The average activation energy for the thermal degradation of WCO was found to be 243.7, 211.23 and 222 kJ mol^?1 for FM, KAS and FWO kinetic methods, respectively. Additionally, the cracking of WCO was studied in a semi-batch reactor under an inert atmosphere and the influences of cracking temperature, time and heating rates on product distribution were investigated. From the reaction, an optimum yield of 72 mass% was obtained at a temperature of 475 °C, time of 180 min and a heating rate of 10 °C min^?1. The physicochemical properties studied were in accordance with ASTM standards.     

Thermoanalytical and NMR investigation of NaBH<Subscript>4</Subscript> × 2H<Subscript>2</Subscript>O thermolysis process

This paper describes the thermal investigations and kinetic analysis regarding the solid-state degradation of three compounds used as mental disorder therapeutic agents (antidepressants), namely amitriptyline, desipramine and imipramine. The study was carried according to ICTAC 2000 recommendations, by using three isoconversional methods, namely Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose and Friedman. The differential method of Friedman indicated multistep degradation, which was later confirmed by the nonparametric kinetic method (NPK). NPK method showed that all three tricyclic antidepressants are degraded by two processes. In terms of apparent activation energies for decomposition, the NPK method indicated 123.4 kJ mol^?1 for imipramine, 112.3 kJ mol^?1 for desipramine and 82.9 kJ mol^?1 for amitriptyline, and the results are in good agreement with the ones suggested by isoconversional methods.     

Study of Brønsted acid site in H-MCM-22 zeolite by temperature-programmed desorption of ammonia

Interaction of ammonia with H-MCM-22 zeolite (Si/Al = 24.5) was investigated by temperature-programmed desorption technique in order to obtain information on thermodynamics of the process. Average activation energy for desorption of ammonia from Brønsted acid sites of H-MCM-22 zeolite was estimated from the data obtained under conditions varying in heating rate and also flow rate of carrier gas. It resulted in value of E _d = 127 kJ mol^?1 for heat rate variation method, whereas flow rate variation led to E _d value of 111 kJ mol^?1. Obtained E _d values are compared with those reported in the literature for other zeolitic materials and discussed in the broader context of zeolite acidity. Comparison of E _d values estimated here for H-MCM-22 zeolite with corresponding data for other protonic zeolites shows that H-MCM-22 displays mediocre/lower activation energy for ammonia compared with other high-silica zeolites.     

Thermodynamic activation parameters of hindered rotation of the CF<Subscript>3</Subscript> group in the 4-nitrophenyltrifluoromethylsulfone radical anion in DMF

The thermodynamic activation parameters of hindered rotation of the CF₃ group in the 4-nitrophenyltrifluoromethylsulfone radical anion in DMF were determined from the temperature dependence of the EPR line widths and spin density distributions calculated by the U-B3LYP method in the 6-31+G* basis set. In the range 293 > T > 199 K, the activation energy of hindered rotation E _F depends on the temperature and changes in the range 9.67 < E _F < 18.95 kJ·mol^?1; the changes in the activation enthalpy and entropy are 7.23 < ΔH ^≠ < 17.30 kJ·mol^?1 and ?53.45 < ΔS ^≠ < ?11.37 J·(mol·K)^?1, respectively. Based on the suggested method for evaluating the inner product of the g tensor and the tensor of anisotropic hfi with the ¹⁴N nucleus for nitrobenzene radical anions in the liquid state we calculated the correlation time and determined the activation energy of rotational diffusion of the 4-nitrophenyltrifluoromethylsulfone radical anion in DMF, E _r = 20.175±0.54 kJ·mol^?1.     

Kinetics of ethylene glycol electrooxidation on the noble metal-based nano-catalysts

A comparative electrooxidation of Eg in the alkaline solution was investigated over Pt, Pd and Au nanoparticle-modified carbon-ceramic electrode. The kinetic parameters of Eg oxidation, i.e., Tafel slope and activation energy (E _a), were determined on the modified electrodes. The lowest E _a value of 8.9 kJ mol^?1 was calculated on Pt|CCE. In continuation, the reaction orders with respect to the Eg and NaOH concentrations on Pd|CCE were found to be 0.4–0.2 and 0.6, respectively. An adsorption equilibrium constant (b) of 22.36 M^?1 and the adsorption Gibbs energy change (ΔG°) of ?7.7 kJ mol^?1 were obtained on Pd|CCE. The chronopotentiometry (CP) and chronoamperometry (CA) results showed that Pd|CCE and then Au|CCE have better performance stability than Pt|CCE for Eg electrooxidation. Additionally, the electrochemical impedance spectroscopy (EIS) suggested faster electron-transfer kinetics on Pt than that on the Pd and Au electrocatalysts.     

Calorimetric study on Ge<Subscript>23</Subscript>Se<Subscript>67</Subscript>Sb<Subscript>10</Subscript>–0.5CsCl glass

The mechanical behavior of Ge₂₃Se₆₇Sb₁₀ glass can be improved by adding CsCl facilitating the nano-crystaline formation. Understanding the crystallization mechanism of chalcogenide glass can help in directing the subsequent annealing processing and tuning the microstructure and physical properties. In this work, 99.5Ge₂₃Se₆₇Sb₁₀–0.5CsCl glass was prepared and its transformation kinetics was investigated under non-isothermal conditions with heating rate up to 400 K min^?1. Using Vogel–Fulcher–Tammann equation, the ideal glass transition temperature was determined as T _0g = 434.1 K. Using the classical JMA theory, the average activation energy and average growth exponent were determined as 135.0 and 2.4 kJ mol^?1, while using the model considering impingements (MCI), the two parameters were determined as 120.9 and 3.2 kJ mol^?1, respectively. Compared to JMA theory, the MCI model can fit the transition curves better, and it shows that the growth mode of the present glass is between two-dimension and three-dimension. By comparing with the result of Ge₂₃Se₆₇Sb₁₀ glass, it is found that addition of CsCl can reduce the growth dimension and activation energy during crystallization.     

Thermal study on decomposition of LiBH4 at non-isothermal and non-equilibrium conditions

Thermal decomposition measurements for lithium borohydride (LiBH₄) are performed at non-isothermal and non-equilibrium conditions by means of differential thermal analysis (DTA). A simplified alternative procedure is introduced for evaluating thermodynamic and kinetic parameters simultaneously using a single set of measurements. Rate constant (k) and enthalpy (ΔH = ?102.1 ± 0.7 kJ mol^?1 LiBH₄) are archived. Temperature dependence for activation energy (E _a) is found taking advantage of Guggenheim–Arrhenius method; the mean activation energy is $ \overline{E}_{a} $  93.9 ± 0.9 kJ mol^?1 LiBH₄ in the range of heating rate β 1–50 K min^?1.     

Applying thermodynamics to digestion/gasification processes: the Attainable Region approach

The research shows theoretical calculations on the thermodynamics of digestion/gasification processes where glucose is used as a surrogate for biomass. The change in Enthalpy (?H) and Gibbs Free Energy (?G) is used to obtain the Attainable Region (AR) that shows the overall thermodynamic limits for digestion/gasification from 1 mol of glucose. Gibbs Free Energy and Enthalpy (G–H) plots were calculated for the temperature range 25–1500 °C. The results show the effect of temperature on the AR for the processes when water is in both liquid and gas states using 25 °C, 1 bar as the reference state. The AR results show that the production of CO, H₂, CH₄ and CO₂ are feasible at all temperatures studied. The minimum Gibbs Free Energy becomes more negative from ?418.68 kJ mol^?1 at 25 °C to ?3024.34 kJ mol^?1 at 1500 °C while the process shifts from exothermic (?141.90 kJ mol^?1) to endothermic (1161.80 kJ mol^?1) for the respective temperatures. Methane and carbon dioxide are favoured products (minimum Gibbs Free Energy) for temperatures up to about 600 °C, and this therefore includes Anaerobic Digestion. The process is exothermic below 500 °C, and thus Anaerobic Digestion requires heat removal. As the temperature continues to increase, hydrogen production becomes more favourable than methane production. The production of gas is endothermic above 500 °C, and it needs a supply of heat that could be done, either by combustion or by electricity (plasma gasification). The calculations show that glucose conversion at temperatures around 700 °C favours the production of carbon dioxide and hydrogen at minimum G. Generally, the results show that the gas from high-temperature gasification (>~800 °C) typically carries the energy mainly in syngas components CO and H₂, whereas at low-temperature gasification (<500 °C) the energy is carried in CH₄. The overall analysis for the temperature range (25–1500 °C) also suggests a close relationship between biogas production/digestion and gasification as biogas production can be referred to as a form of low-temperature gasification.     

Binding interaction and conformational changes of human serum albumin with ranitidine studied by spectroscopic and time-resolved fluorescence methods

This study was designed to examine the interaction of histamine H₂-receptor antagonist drug ranitidine (RTN) with human serum albumin by multi-spectroscopic methods. The experimental results showed the involvement of dynamic quenching mechanism which was further confirmed by lifetime spectral studies. The binding constants (K _a) at three temperatures (288, 298, and 308 K) were 2.058 ± 0.020, 4.160 ± 0.010 and 6.801 ± 0.011 × 10⁴ dm³ mol^?1, respectively, and the number of binding sites (m) were 1.169, respectively; thermodynamic parameters ΔH ⁰ (44.152 ± 0.047 kJ mol^?1), ΔG ⁰ (?26.214 ± 0.040 kJ mol^?1), and ΔS ⁰ (236.130 ± 0.025 J K^?1 mol^?1) were calculated. The distance r between donor and acceptor was obtained (r = 3.40 nm) according to the Förster theory of non-radiative energy transfer. Synchronous fluorescence, CD, AFM and 3D fluorescence spectral results revealed the changes in secondary structure of the protein upon interaction with RTN. A molecular modeling study further confirmed the binding mode obtained by the experimental studies.     

Study of the gadolinium sorption on the C100 ion-exchange resin for the development of the antineutrino detector targets

Adsorption of the gadolinium from H₂O and HCl solutions on the ion-exchange resin C100 is investigated. The experiments were carried out by varying the acidity of the liquid phase, the amount of sorbent, and the temperature. The maximal sorption of the ions Gd³⁺ is observed from the solution 0–0.2 M HCl under optimal conditions, the sorption reaches more than 99.5%. Sorption of Gd³⁺ on C100 from H₂O solution occurs most intensively during the first 3 min then for 30 min the system smoothly comes to equilibrium. The maximal sorption capacity of the resin C100 amounted to 1.2 ± 0.1 mmol g^?1. The thermodynamic parameters of sorption: ΔG = ? 24.20 kJ mol^?1, ΔS = ? 90.27 J mol^?1 K^?1, ?H = ? 50.93 kJ mol^?1 were evaluated. It is shown that the sorption of gadolinium on the ion-exchange resin C100 is described by models of kinetically pseudo-first and pseudo-second order. It is established that the Gd³⁺ sorption on the C100 resin is reversible second order chemical reaction.     

Non-isothermal crystallization kinetics of a Si–Ca–P–Mg bioactive glass

In this work, the crystallization process of a SiO₂–3CaO·P₂O₅–MgO glass was studied by non-isothermal measurements using differential thermal analysis carried out at various heating rates. X-ray diffraction at room and high temperature was used to identify and follow the evolution of crystalline phases with temperature. The activation energy associated with glass transition, (E _g), the activation energy for the crystallization of the primary crystalline phase (E _c), and the Avrami exponent (n) were determined under non-isothermal conditions using different equations, namely from Kissinger, Matusita & Sakka, and Osawa. A complex crystallization process was observed with associated activation energies reflecting the change of behavior during in situ crystal precipitation. It was found that the crystallization process was affected by the fraction of crystallization, (x), giving rise to decreasing activation energy values, E _c(x), with the increase of x. Values ranging from about 580 kJ mol^?1 for the lower crystallized volume fraction to about 480 kJ mol^?1 for volume fractions higher than 80 % were found. The Avrami exponents, calculated for the crystallization process at a constant heating rate of 10 °C min^?1, increased with the crystallized fraction, from 1.6 to 2, indicating that the number of nucleant sites is temperature dependent and that crystals grow as near needle-like structures.     

Thermogravimetric analysis of lignocellulosic and microalgae biomasses and their blends during combustion

Thermogravimetric analysis was used to study and compare the combustion of different blends of corn bioresidues with sunflower, rape and algae bioresidues. Non-isothermal thermogravimetric data were used to obtain the combustion kinetics of these bioresidues. This paper reports on the application of the Vyazovkin and Ozawa–Flynn–Wall isoconversional methods for the evaluation of kinetic parameters (energy activation, pre-exponential factor and order of reaction) for the combustion of the biomasses studied. Differences were found in the TG curves in accordance with the proximate analysis results for the cellulose, hemicellulose and lignin content of biomasses. The activation energy obtained from combustion (E ~ 151.6 kJ mol^?1) was lower than that from the blends (similar values were obtained for corn–sunflower, E ~ 160.5 kJ mol^?1 and corn–rape, E ~ 156.9 kJ mol^?1) whereas the activation energy obtained from the microalgae was higher (E ~ 171.5 kJ mol^?1). Both the Vyazovkin and Ozawa–Flynn–Wall methods yielded similar results.     

Studies on the thermal behavior and decomposition kinetic of drugs cetirizine and simvastatin

Understanding the response of drugs and their formulations to thermal stresses is an integral part of the development of stable medicinal products. In the present study, the thermal degradation of two drug samples (cetirizine and simvastatin) was determined by differential scanning calorimetery (DSC) and simultaneous thermogravimetery/differential thermal analysis (TG/DTA) techniques. The results of TG analysis revealed that the main thermal degradation for the cetirizine occurs during two temperature ranges of 165–227 and 247–402 °C. The TG/DTA analysis of simvastatin indicates that this drug melts (at about 143 °C) before it decomposes. The main thermal degradation for the simvastatin occurs during two endothermic behaviors in the temperature ranges of 238–308 and 308–414 °C. The influence of the heating rate (5, 10, 15, and 20 °C min^?1) on the DSC behavior of both the drug samples was verified. The results showed that as the heating rate was increased, decomposition temperatures of the compounds were increased. Also, the kinetic parameters such as activation energy and frequency factor for the compounds were obtained from the DSC data by non-isothermal methods proposed by ASTM E696 and Ozawa. Based on the values of activation energy obtained by ASTM E696 method, the values of activation energy for cetirizine and simvastatin were 120.8 and 170.9 kJ mol^?1, respectively. Finally, the values of ΔS ^#, ΔH ^#, and ΔG ^# of their decomposition reaction were calculated.     

Global and local interactions in the structure of crystalline 7-(diethylamino)-2-(2-oxo-2<Emphasis Type="Italic">H</Emphasis>-chromen-3-yl)chromenium perchlorate

Computational methods were used to calculate the crystal lattice energy reflecting global interactions, predominantly long-range electrostatic interactions between ions, as well as the energy of selected specific local C–H···O, C–H···π and π···π interactions found in synthesized 7-(diethylamino)-2-(2-oxo-2H-chromen-3-yl)chromenium perchlorate, the structure of which was determined by X-ray crystallography. Local interactions occurring between specific sites of molecules, amounting to a few tens of kJ mol^?1, most likely account for the mutual arrangement of molecular ions, whereas global ones, exceeding half-a-thousand kJ mol^?1, are responsible for the thermodynamic stability of the compound investigated in the crystalline solid phase, whose potential applications are briefly outlined.     

Kinetic and thermodynamic parameters of volatilization of biodiesel from babassu, palm oil and mineral diesel by thermogravimetric analysis (TG)

The boiling point and volatility are important properties for fuels, as it is for quality control of the industry of petroleum diesel and biofuels. In addition, through the volatility is possible to predict properties, such as vapor pressure, density, latent heat, heat of vaporization, viscosity, and surface tension of biodiesel. From thermogravimetry analysis it is possible to find the kinetic parameters (activation energy, pre-exponential factor, and reaction order), of thermally simulated processes, like volatilization. With the kinetic parameters, it is possible to obtain the thermodynamic parameters by mathematical formula. For the kinetic parameters, the minor values of activation energy were found for mineral diesel (E = 49.38 kJ mol^?1), followed by babassu biodiesel (E = 76.37 kJ mol^?1), and palm biodiesel (E = 87.00 kJ mol^?1). Between the two biofuels studied, the babassu biodiesel has the higher minor value of activation energy. The thermodynamics parameters of babassu biodiesel are, ΔS = ?129.12 J mol^?1 K^?1, ΔH = +80.38 kJ mol^?1 and ΔG = +142.74 kJ mol^?1. For palm biodiesel ΔS = ?119.26 J mol^?1 K^?1, ΔH = + 90.53 kJ mol^?1 and ΔG = +141.21 kJ mol^?1, and for diesel ΔS = ?131.3 J mol^?1 K^?1, ΔH = +53.29 kJ mol^?1 and ΔG = +115.13 kJ mol^?1. The kinetic thermal analysis shows that all E, ΔH, and ΔG values are positive and ΔS values are negative, consequently, all thermodynamic parameters indicate non-spontaneous processes of volatilization for all the fuels studied.     

Kinetic analysis of co-pyrolysis of cellulose and polypropylene

The present research work focuses on understanding the kinetics and mechanism of co-pyrolysis of cellulose, a major constituent of biomass, and polypropylene (PP) that is abundantly present in waste plastics. Co-pyrolysis of cellulose and PP of different compositions, viz., 100:0, 80:20, 60:40, 40:60, 20:80, and 0:100 (mass%/mass%), was carried out in a thermogravimetric analyzer at various heating rates from 5 to 180 K min^?1. The kinetics of slow to medium heating rate pyrolysis was analyzed using first Kissinger and Kissinger–Akahira–Sunose techniques. Cellulose and PP decomposition occurred in two distinct temperature regimes, viz., 575–650 and 675–775 K, respectively. However, apparent activation energies of thermal decomposition of the mixtures clearly indicated the presence of interaction between cellulose and PP. The presence of cellulose in the mixture decreased the apparent activation energy of PP decomposition from 210 to 120 kJ mol^?1, while the presence of PP did not affect the apparent activation energy of cellulose decomposition (E _a = 158 ± 3 kJ mol^?1). A significant decrease in apparent activation energy was observed in the conversion regime corresponding to the completion of cellulose pyrolysis and beginning of PP pyrolysis. Differential scanning calorimetry data clearly showed the shift of exothermic char formation to higher temperatures with PP incorporation in the mixture. The presence of PP also resulted in reduction of final char content. Based on the above analyses, a new interaction step that involves a bimolecular reaction of activated PP with volatiles from cellulose pyrolysis to form interaction products and char is proposed, and the rate limiting steps for char formation are clearly identified.     

New findings on thermal degradation properties of fluoropolymers

In this paper, the thermal degradation properties of Viton A and Fluorel are investigated by both isoconversional and combined kinetic analysis methods using non-isothermal thermogravimetry technique. It has been found that the heating rate has little affect on the degradation residue of Fluorel and Viton A, where around 1.3% char was formed for Fluorel and 3.5% for Viton A. Different from the literature, the decomposition of Viton A should be considered as an overlapped dehydrofluorination and carbon chain scission process, with activation energy of 214 ± 11 and 268 ± 13 kJ mol^?1, respectively. The effect of dehydrofluorination on degradation of Fluorel is not so significant due to low content of H, and hence, it could be considered as a single-step mechanism with average activation energy of 264 ± 14 kJ mol^?1. The thermal stability of Fluorel is much better than that of Viton A, and the predicted half-life is around 218 min for Fluorel and 49 min for Viton A at 420 °C, which are consistent with experimental values. If using a single-step model as in the literature for Viton A, its half-life at 420 °C would be underestimated for >20%.     

Synthesis, structure analysis and thermodynamics of [Ni(H2O)4(TO)2](NO3)2·2H2O (TO = 1,2,4-triazole-5-one)

A novel complex [Ni(H₂O)₄(TO)₂](NO₃)₂·2H₂O (TO = 1,2,4-triazole-5-one) was synthesized and structurally characterized by X-ray crystal diffraction analysis. The decomposition reaction kinetic of the complex was studied using TG-DTG. A multiple heating rate method was utilized to determine the apparent activation energy (E _a) and pre-exponential constant (A) of the former two decomposition stages, and the values are 109.2 kJ mol^?1, 10^13.80 s^?1; 108.0 kJ mol^?1, 10^23.23 s^?1, respectively. The critical temperature of thermal explosion, the entropy of activation (ΔS ^≠), enthalpy of activation (ΔH ^≠) and the free energy of activation (ΔG ^≠) of the initial two decomposition stages of the complex were also calculated. The standard enthalpy of formation of the new complex was determined as being ?1464.55 ± 1.70 kJ mol^?1 by a rotating-bomb calorimeter.