Demystification of luminescence properties and the near imperceptible thermal quenching of Sm3+-doped tungstate phosphors.

Ultra-high thermally stable Ca2MgWO6:xSm3+ (x = 0.5, 0.75, 1, 1.25, and 1.5 mol%) double perovskite phosphors were synthesized through solid-state reaction method. Product formation was confirmed by comparing the X-ray diffraction (XRD) patterns of the phosphors with the standard reference file. The structural, morphological, thermal, and optical properties of the prepared phosphor were examined in detail using XRD, Fourier transform infrared spectra, scanning electron microscopy, diffused reflectance spectra, thermogravimetric analysis (TGA), photoluminescence emission, and temperature-dependent PLE (TDPL). It was seen that the phosphor exhibited emission in the reddish region for the near-ultraviolet excitation with moderate Colour Rendering Index values and high colour purity. The optimized phosphor (x = 1.25 mol%) was found to possess a direct optical band gap of 3.31 eV. TGA studies showed the astonishing thermal stability of the optimized phosphor. Additionally, near-zero thermal quenching was seen in TDPL due to elevated phonon-assisted radiative transition. Furthermore, the anti-Stokes and Stokes emission peaks were found to be sensitive toward the temperature change and followed a Boltzmann-type distribution. All these marked properties will make the prepared phosphors a suitable candidate for multifield applications and a fascinating material for further development.

Study of biphasic calcium phosphate (BCP) ceramics of tilapia fish bones by age.

Biphasic calcium phosphate (BCP), consisting of bioceramics such as HAp + ß-TCP and Ca10(PO4)6(OH)2 + Ca3(PO4)2, is a popular choice for optimizing performance due to its superior biological reabsorption and osseointegration. In this study, BCP was produced by calcining the bones of tilapia fish (Oreochromis niloticus) reared in net cages and slaughtered at an age ranging from 15 to 420 days. The bones were cleaned and dried, calcined at 900 °C for 8 h, and then subjected to high-energy grinding for 3 h to produce BCP powders. After the calcination process, the crystalline phase's hydroxyapatite (HAp) and/or beta-tricalcium phosphate (ß-TCP) were present in the composition of the bioceramic. The age-dependent variation in phase composition was confirmed by complementary vibrational spectroscopy techniques, revealing characteristic peaks and bands of the bioceramic. This variation was marked by an increase in HAp phase and a decrease in ß-TCP phase. Thermogravimetric Analysis (TGA) and Differential Thermal Analysis (DTA) from 25 to 1400 °C showed the characteristic mass losses of the material, with a greater loss observed for younger fish, indicating the complete removal of organic components at temperatures above 600 °C. Comparison of the results obtained by X-Ray Diffraction (XRD) and Rietveld refinement with Raman spectroscopy showed excellent agreement. These results showed that with temperature and environment control and adequate fish feeding, it is possible to achieve the desired amounts of each phase by choosing the ideal age of the fish. This bioceramic enables precise measurement of HAp and ß-TCP concentrations and Ca/P molar ratio, suitable for medical orthopedics and dentistry.

Extraction of lignin-containing nanocellulose fibrils from date palm waste using a green solvent.

Lignin-containing nanocellulose (LNC) is a compelling alternative to traditional nanocellulose (NC), it offers enhanced yields and a reduction in the demand for toxic chemicals. This research involves the isolation of LNC from date palm waste using a green hydrolysis process and its subsequent characterization. The potential of using ionic liquids (ILs) as green solvents to isolate LNC has not yet been explored. Our findings suggest that 1-ethyl-3-methylimidazolium chloride ([Emim]Cl) can hydrolyze partially delignified and unbleached lignocellulose, achieving LNC synthesis. The obtained LNC showed a higher yield than its NC counterpart and exhibited rod-shaped fibers with nanoscale diameters and micrometer lengths, indicating a high aspect ratio. Dynamic Light Scattering (DLS) results indicate average particle sizes of 143.20 nm for NC and 282.30 nm for LNC, with a narrow particle size distribution conforming their monodisperse behavior. Thermogravimetric analysis and differential scanning calorimetry revealed high thermal stability (initial degradation temperature = 222.50 °C and glass transition temperature = 84.45°C) of LNC. Moreover, the obtained LNC fibers were crystalline (crystallinity index = 52.76 %). Their activation energy (124.95 kJ/mol) was determined using the Coats-Redfern method by employing eight solid-state diffusion models. Overall, this study motivates the use of ILs as green solvents to produce lignocellulose derivatives that are suitable for various applications.

Thermogravimetric experiments based prediction of biomass pyrolysis behavior: A comparison of typical machine learning regression models in Scikit-learn.

A variety of machine learning (ML) models have been extensively utilized in predicting biomass pyrolysis owing to their prowess in deciphering complex non-linear relationships between inputs and outputs, but there is still a lack of consensus on the optimal methods. This study elaborates on the development, optimization, and evaluation of three ML methodologies, namely, artificial neural networks, random forest (RF), and support vector machines, aimed to determine the optimal model for accurate prediction of biomass pyrolysis behavior using thermogravimetric data. This work assesses the utility of thermal data derived from these models in the computation of kinetic and thermodynamic parameters, alongside an analysis of their statistical performance. Eventually, the RF model exhibits superior physical interpretability and the least discrepancy in predicting kinetic and thermodynamic parameters. Furthermore, a feature importance analysis conducted within the RF model framework quantitatively reveals that temperature and heating rate account for 98.5 % and 1.5 %, respectively.

The relevant effect of marine salt and epiphytes on Posidonia oceanica waste pyrolysis: Removal of SO2/HCl emissions and promotion of O/HCOOH formation.

Significant quantities of Posidonia oceanica deposit on some beaches and coastlines every year, which generates high costs associated with the disposal of this waste. Pyrolysis may be an adequate way for its valorization. However, it would imply to know how the process takes place and if the removal of its natural detrital inorganic matter (epiphytes, marine salt and sand) is necessary, which are the objectives of this research. Pyrolysis by thermogravimetry-mass spectrometry was carried out on both the washed and unwashed samples. During this waste pyrolysis, the following occurs: (i) the high alkali metal chloride content promotes fragmentation reactions of carbohydrates and O formation, which increases HCOOH intensities at temperatures between 250 and 360 °C; (ii) from 500 °C to 650 °C, Fe2O3 and decomposition of carbonates seem to be involved in reactions that produce O release and steam and CO2 reforming of hydrocarbons and oxygenated organic compounds with H2 generation; (iii) from 650 °C to 750 °C, Fe2O3, high alkali metal content and carbonate decomposition generate char gasification, an increase in O release, SO2 capture and HCOOH formation. In general, the abundance of inorganic matter (chlorides, carbonates, etc.) minimizes the release of various compounds during pyrolysis, including SO2 and HCl, while increasing HCOOH production. Thus, this high content of inorganic matter may represent an advantage for its pyrolysis, producing value-added chemical products with a reduced environmental impact. Therefore, this study may be the starting point for defining the optimal pyrolysis conditions for this waste valorisation.

Pyrolysis of Euphorbia Rigida: A study on thermal characterizations, kinetics, thermodynamics via TG-FTIR analysis.

Euphorbia Rigida (E. Rigida), a lignocellulosic biomass with low ash content, is a suitable feedstock for pyrolysis. This work investigated the physicochemical characteristics and thermokinetic analysis of E. Rigida pyrolysis by using isoconversional and master plots methods. Ultimate and proximate analyses and oxygen bomb calorimeter were used to determine the physicochemical parameters. The activation energies were calculated using model-free methods (KAS, Friedman and Starink) and were found as 184, 178 and 185 kJ/mol, respectively. Using Fraser-Suzuki deconvolution, pseudo-components were also calculated and the active pyrolysis region was divided into three zones. The master plots showed that reaction order mechanisms (Fn) were effective in Zone I, and diffusion mechanisms (Dn) were well matched in Zone II and Zone III. The thermodynamic parameters (ΔH, ΔG and ΔS) were calculated and according to these results, E. Rigida pyrolysis was an endothermic and non-spontaneous process.

Gelatine Blends Modified with Polysaccharides: A Potential Alternative to Non-Degradable Plastics.

Non-degradable plastics of petrochemical origin are a contemporary problem of society. Due to the large amount of plastic waste, there are problems with their disposal or storage, where the most common types of plastic waste are disposable tableware, bags, packaging, bottles, and containers, and not all of them can be recycled. Due to growing ecological awareness, interest in the topics of biodegradable materials suitable for disposable items has begun to reduce the consumption of non-degradable plastics. An example of such materials are biodegradable biopolymers and their derivatives, which can be used to create the so-called bioplastics and biopolymer blends. In this article, gelatine blends modified with polysaccharides (e.g., agarose or carrageenan) were created and tested in order to obtain a stable biopolymer coating. Various techniques were used to characterize the resulting bioplastics, including Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA)/differential scanning calorimetry (DSC), contact angle measurements, and surface energy characterization. The influence of thermal and microbiological degradation on the properties of the blends was also investigated. From the analysis, it can be observed that the addition of agarose increased the hardness of the mixture by 27% compared to the control sample without the addition of polysaccharides. In addition, there was an increase in the surface energy (24%), softening point (15%), and glass transition temperature (14%) compared to the control sample. The addition of starch to the gelatine matrix increased the softening point by 15% and the glass transition temperature by 6%. After aging, both compounds showed an increase in hardness of 26% and a decrease in tensile strength of 60%. This offers an opportunity as application materials in the form of biopolymer coatings, dietary supplements, skin care products, short-term and single-contact decorative elements, food, medical, floriculture, and decorative industries.

Novel chitosan-based smart bio-nanocomposite films incorporating TiO2 nanoparticles for white bread preservation.

Chitosan (CS)-based bio-nanocomposite food packaging films were prepared via solvent-casting method by incorporating a unique combination of additives and fillers, including polyvinyl alcohol (PVA), glycerol, Tween 80, castor oil (CO), and nano titanium dioxide (TiO2) in various proportions to enhance film properties. For a comprehensive analysis of the synthesized films, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), tensile testing, field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), and UV-vis spectrophotometry were employed. Furthermore, the antimicrobial efficacy of the films against S. aureus, E. coli, and A. niger was examined to assess their potential to preserve food from foodborne pathogens. The results claimed that the inclusion of castor oil and TiO2 nanoparticles considerably improved antimicrobial properties, UV-vis light barrier properties, thermal stability, optical transparency, and mechanical strength of the films, while reducing their water solubility, moisture content, water vapor and oxygen permeability. Based on the overall analysis, CS/PVA/CO/TiO2-0.3 film can be selected as the optimal one for practical applications. Furthermore, the practical application of the optimum film was evaluated using white bread as a model food product. The modified film successfully extended the shelf life of bread to 10 days, surpassing the performance of commercial LDPE packaging (6 days), and showed promising attributes for applications in the food packaging sector. These films exhibit superior antimicrobial properties, improved mechanical strength, and extended shelf life for food products, marking a sustainable and efficient alternative to conventional plastic packaging in both scientific research and industrial applications.

Exploring the synergistic effect of carboxymethyl cellulose and chitosan in enhancing thermal stability of polyurethanes through statistical mixture design approach.

The thermal stability of polyurethanes, known for its limitations, was addressed in this research by seeking improvement through the introduction of carbohydrate-based chain extenders. In this research paper, we systematically sought to improve the thermal resistance of polyurethanes by incorporating carboxymethyl cellulose and chitosan, representing a pioneering application of the mixture design approach in their preparation. In this synthesis, hydroxyl-terminated polybutadiene and isophorone diisocyanate (IPDI) were reacted to prepare -NCO terminated prepolymer, which was subsequently reacted with varying mole ratios of CMC and CSN to develop a series of five PU samples. The prepared PU samples were characterized using the Fourier-transformed infrared spectroscopic technique. Thermal pyrolysis of PU samples was examined using thermal gravimetric analysis (TGA). It was observed that, among all the samples, PUS-3 showed remarkable thermal stability over a wide temperature range. A comprehensive statistical analysis was conducted to substantiate the experimental findings. It was estimated that CMC and CSN significantly enhance the thermal stability of the samples when involved in an interaction fashion. The ANOVA Table for the mixture design demonstrates that over 90 % of the total variation in thermal stability is explained by the mixture model across a wide temperature range. Moreover, PSU-3 exhibited 4 % more thermal stability over a wide range of temperatures on average, as compared to contemporary samples.

Thermo-chemical behaviour of Dunaliella salina biomass and valorising their biochar for naphthalene removal from aqueous rural environment.

Thermo-chemical behavior of a microalgal biomass; Dunaliella salina was investigated through thermo-gravimetric analyses. Fully-grown D. salina biomass were subjected for biochar conversion using pyrolytic treatment at three distinct heating rates such as 2.5, 5, and 15 °C min-1. The kinetic appraisals were explained by using model-free kinetics viz., Kissinger-Akahira-Sanose, Flynn-Waal-Ozawa and Starink iso-conversional correlations with concomitant evaluation of activation energies (Ea). The Ea value is 194.2 kJ mol-1 at 90% conversion in FWO model, which is higher as compared to other two models. Moisture, volatile substances, and other biochemical components of the biomass were volatilized between 400 and 1000 K in two separate thermo-chemical breakdown regimes. Microscopic and surface characterization analyses were carried out to elucidate the elemental and morphological characteristics of the biomass and biochar. Further, the proficiency of the prepared biochar was tested for removing naphthalene from the watery media. The novelty of the present study lies in extending the applicability of biochar prepared from D. salina for the removal of a model polyaromatic hydrocarbon, naphthalene.

Interaction between lignin and cellulose during the pyrolysis process.

The hierarchical and heterogeneous structures and the interactions between biomass components within cell walls are closely related to the pyrolysis characteristics. In this work, thermogravimetric analysis (TGA) and pyrolysis kinetics analysis were used to investigate the pyrolysis characteristics of windmill palm (Trachycarpus fortunei (Hook.) H. Wendl.) culm and silk after delignification. The results demonstrate cellulose pyrolysis temperature of silk is much higher than that of culm, attributed to the higher lignin content of the former. After delignification, the cellulose pyrolysis temperature of silk decreased by 48 °C, which is much higher than that of culm by 18 °C, suggesting a strong interaction between lignin and cellulose during the pyrolysis process. Futhermore, pyrolysis kinetics analysis also found that the frequency factor of slik and culm increased by 129 % and 26 %, respectively, attributed to the disappearance of the carbon layer formed by lignin pyrolysis process. And, differ in lignin content is responsible for the discrepancy of frequency factor increase. In conclusion, we propose a mechanism model for lignin hindering cellulose pyrolysis, which is of great significance for understanding the pyrolysis interactions of biomass components in complex supramolecular cell wall.

Cassava starch esterification with formic acid for fabrication of electrospun fibers.

Formic acid is utilized to induce esterification and chemical gelatinization in starch, particularly in the fabrication of electrospun fibers for nanomaterial production. This study investigated the impact of different concentrations (15, 20, 25, and 30 %) of cassava starch and formic acid as a solvent on the characteristics of the resultant polymeric solutions and electrospun fibers. Morphology, size distribution, thermogravimetric properties, diffraction patterns, and relative crystallinity were evaluated for the electrospun fibers. The amylose content of starch varied from 16.5 to 23.7 %, decreasing with esterification, achieving a degree of substitution of approximately 0.93. The solution-rheology exhibited elastic behavior, with viscosity increasing as starch concentration increased, hindering the fabrication of fibers at 25 and 30 % starch. Successful electrospun fibers were formed using 15 % and 20 % starch, displaying homogeneous morphologies with mean diameters of 165 nm and 301 nm, respectively. Esterification influenced thermogravimetric properties, leading to fibers with reduced degradation temperatures and mass loss compared to native starches. The electrospun fibers presented an amorphous structure, indicating a drastic reduction in relative crystallinity from 35.2 % in native starch to 8.5 % for esterified starches. This study highlights the intricate relationship between starch concentration, esterification, and solution viscosity, affecting the electrospinnability and properties of starch-polymeric solutions.

Sustained-release nitrogen fertilizer delivery systems based on carboxymethyl cellulose-grafted polyacrylamide: Swelling and release kinetics.

Sustained or controlled-release delivery systems can enhance functions such as nutrient usage; minimize soil contamination, and reduce the required fertilizer dose. This paper reports the development of a carboxymethyl cellulose-g-polyacrylamide copolymer (CMC-g-PAM) as a sustained and slow-release fertilizer carrier for urea. The developed copolymer was characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), and thermo gravimetric analysis (TG). The grafting process increased the activation energy of CMC from 0.1521 to 0.5952 J/mol with a higher loading percentage of 72.140.85% using a 15% urea solution. The swelling ratio is significantly dependent on the pH. The maximum swelling ratio of 1199.58% at pH 9. However, Swelling follows a pseudo-first-order reaction with the maximum swelling ratio in a saline of 349.76%. The CMC-g-PAM copolymer loaded with urea exhibited sustained and slow release, with the maximum cumulative percentage of 69.12% at pH 9 and 38.94% in saline. Urea release from the CMC-g-PAM copolymer followed the first-order, Fickian, and biexponential biphasic release mechanisms. The release of the CMC-g-PAM copolymer loaded with urea is a complicated process governed by diffusion and a biphasic releasing profile.

Progress and challenges in valorisation of biomass waste from ornamental trees pruning through pyrolysis processes. Prospects in the bioenergy sector.

Nowadays, the scarcity of energy resources is promoting the search for alternative energy sources, boosting interest in the use of forest lignocellulosic residue in the energy sector. In this study, the focus is on the energy recovery from two lignocellulosic residues originated during the pruning of ornamental trees (Horse Chestnut, CI, and False Acacia, FA). Both conventional and flash pyrolysis techniques were applied. The experimental pyrolysis variables were obtained from the study of the thermal behaviour of the pruning residues in thermogravimetric analysis. It was carried out under 5 heating rates and kinetic parameters were estimated using Flynn-Wall-Ozawa method. Results denoted higher maximum mass loss rate values for the same release temperature regions under FA experiments. Also, FA samples had lower final residues for the processes. However, activation energy values were so close for both species. FA was also linked to the faster reactions according frequency factor outcomes. Conventional pyrolysis of pruning residues was carried out in a horizontal oven of original design at a heating rate of 25 °C/min, at 750 °C and 60 min of permanence at that temperature; flash pyrolysis was tested in that oven at 750 and 850 °C. In these pyrolysis processes, three fractions were obtained: bio-char, bio-oil and gas. The physicochemical attributes of the bio-chars suggested their potential utility as biofuels (28.4-29.8 MJ/kg), adsorbent precursors or soil additives. Conventional pyrolysis bio-oils had a dominant monoaromatic hydrocarbons nature, with phenols being the most abundant (≥60%), while flash bio-oils contain mainly polycyclic aromatic hydrocarbons. Conventional pyrolysis gases contained up to 60 vol% of CO2; flash pyrolysis gases had high combustible gas content (CO, CH4, H2) and a low CO2 content (<25 vol%). As a result, their calorific value (18.06 MJ/kg) exhibited a threefold increase compared to the gas produced through conventional pyrolysis (6.04 MJ/kg).

Artificial neural network-assisted thermogravimetric analysis of thermal degradation in combustion reactions: A study across diverse organic samples.

During gasification the kinetic and thermodynamic parameter depend on both the feedstock and the process conditions. As a result, one needs to enhance the understanding of how to model numerically these parameters using thermogravimetric analyzer. Consequently, there exists a pressing need to computationally devise gasification model that can efficiently account to thermodynamic and kinetic parameter from thermogravimetric data. In this study, we numerically model gasification process kinetic and thermodynamic parameters, which vary with feedstock and operational conditions. Our novel approach involves creating an ANN model in MATLAB using a carefully optimized 8-20-20-10-1 architecture. Based on thermogravimetric analyzer (TGA) data, this model uniquely predicts critical kinetic (activation energy, pre-exponential factor) and thermodynamic parameters (entropy, enthalpy, Gibbs free energy, ignition index, boiling temperature). Our ANN model, trained on over 80 diverse samples with the Levenberg-Marquardt algorithm, excels at prediction, with an MSE of 6.185e-6 and an R2 value exceeding 0.9996, ensuring highly accurate estimates. Based on time, temperature, heating rate, and elemental composition, it accurately predicts thermal degradation. The model can predict TGA curves for many materials, demonstrating its versatility. For instance, it accurately estimates the activation energy for pure glycerol at 73.84 kJ/mol, crude glycerol at 67.55 kJ/mol, 12.12 kJ/mol for coal, and 111.3 kJ/mol for wood. These results, particularly for Kissinger-validated glycerol, demonstrate the model's versatility and efficacy in various gasification scenarios, making it a valuable tool for thermochemical conversion studies.

Exploring multistep bischofite waste pyrolysis: insights from advanced kinetic analysis and thermogravimetric techniques.

Pyrolysis technology is crucial for realizing waste bischofite resource utilization. However, previous studies overlooked the complexity of multistep pyrolysis, resulting in a lack of thorough knowledge of the pyrolysis behavior and kinetics. The pyrolysis products were characterized using XRD and FTIR to indicate the bischofite pyrolysis behavior. Additionally, the multistep kinetics was studied using the segmented single-step reaction (SSSR) and Fraser-Suzuki combined kinetic (FSCK) methods. The results show that the bischofite pyrolysis is divided into dehydration and hydrolysis. The former refers to removing crystalline water from MgCl2·nH2O (n = 4,6). At the same time, the latter is related to the removal of HCl, characterized by the strengthening of the Mg-O bond in the FTIR analysis and the emergence of MgOHCl·1.5H2O in the XRD examination. The two main stages are divided into three dehydration reactions (D-1, D-2, D-3) and three hydrolysis reactions (H-1, H-2, H-3) by DTG-DDTG or Fraser-Suzuki deconvolution. Compared with the SSSR method, the FSCK method has improved model repeatability for multistep kinetic parameters. Following Fraser-Suzuki deconvolution, the FSCK method creates almost the same activation energy results when using the Friedman (FR), Kissinger-Akahira-Sunose (KAS), and Vyazovkin (VZK). This work provides fundamental data to promote the maximizing waste bischofite resource utilization.

Investigation of the evolved pyrolytic products and energy potential of Bagasse: experimental, kinetic, thermodynamic and boosted regression trees analysis.

This study explored bagasse's energy potential grown using treated industrial wastewater through various analyses, experimental, kinetic, thermodynamic, and machine learning boosted regression tree methods. Thermogravimetry was employed to determine thermal degradation characteristics, varying the heating rate from 10 to 30 °C/min. The primary pyrolysis products from bagasse are H2, CH4, H2O, CO2, and hydrocarbons. Kinetic parameters were estimated using three model-free methods, yielding activation energies of approximately 245.98 kJ mol-1, 247.58 kJ mol-1, and 244.69 kJ mol-1. Thermodynamic parameters demonstrated the feasibility and reactivity of pyrolysis with ΔH ≈ 240.72 kJ mol-1, ΔG ≈ 162.87 kJ mol-1, and ΔS ≈ 165.35 J mol-1 K-1. The distribution of activation energy was analyzed using the multiple distributed activation energy model. Lastly, boosted regression trees predicted thermal degradation successfully, with an R2 of 0.9943. Therefore, bagasse's potential as an eco-friendly alternative to fossil fuels promotes waste utilization and carbon footprint reduction.

Kinetic reaction mechanism of lignocellulosic biomass oxidative pyrolysis based on combined kinetics.

The kinetics knowledge of lignocellulosic biomass decomposition is essential to develop efficient thermochemical conversion technology. However, the simplification of reaction mechanisms in existing oxidative pyrolysis studies largely compromises the application of kinetic models. To explore more exact kinetic parameters and reaction mechanism of lignocellulosic biomass oxidative pyrolysis, an updated oxidative pyrolysis kinetic model (seven-step reaction combined kinetics model) coupled with an optimization algorithm is proposed. Based on a series of thermogravimetric experiments in an air atmosphere, the extra oxidative pyrolysis kinetic parameters are obtained by the Shuffled Complex Evolution method. The proposed kinetic model is validated based on the degradation process of each component (hemicellulose, cellulose, and lignin). Furthermore, the obtained kinetic parameters are applied to predict the oxidative pyrolysis behavior, and the predicted mass loss rate is in good agreement with the experimental data. Eventually, according to the key combined kinetics parameters, it is found that the oxidative pyrolysis mechanisms of hemicellulose, cellulose, and lignin correspond to the power law, nucleation & growth, and chemical reaction order, respectively, while the combustion of char corresponds to the reaction order mechanism.

Physicochemical Characterization of Woody Lignocellulosic Biomass and Charcoal for Bio-energy Heat Generation.

Biomass and its interactions for heat generation have received little attention. In this study, the woody biomass materials were Prosopis africana (PA), Harungana madascariences (HM), Vitrllaria paradoxa (VP), and Afzelia africana (AA). The composition (extractives, carbohydrate, and lignin) of the biomass was determined. The biomass was converted to charcoal in a traditional kiln. A thermo-kinetic examination of the charcoal samples was carried out. The kinetic parameters and potential reaction mechanisms involved in the decomposition process were both obtained using the integral (Flynn-Wall Ozawa) isoconversional methods in conjunction with the Coats-Redfern approach. The activation energy profiles for the charcoal samples in oxidizing atmospheres were 548 kJ/mol for AA, 274 kJ/mol for VP, 548 kJ/mol for PA, and 274 kJ/mol for HM. All charcoal samples underwent comprehensive, multi-step, complex reaction pathways for thermal degradation. The charcoal samples exhibit not only great potential for biochemical extraction but also for bioenergy applications. The significant amount of combustion characteristics in the raw biomass and charcoal samples indicates that each type of wood charcoal produced has more fixed carbon, less ash, and less volatile matter, all of which are desirable for the thermo-chemical conversion of biomass for the production of heat.

Pyrolysis of municipal solid waste: A kinetic study through multi-step reaction models.

The present study endeavors to establish a comprehensive kinetic analysis of Municipal Solid Waste residue pyrolysis. As the sample exhibits four distinct degradation stages, it has been carried out by adopting a multi-step process behavior. Different approaches have been compared, including five isoconversional methods (Kissinger-Akahira-Sunose, Ozawa-Flynn-Wall, Starink, Friedman and Advanced integral Vyazovkin), Mathematical Deconvolution Analysis, and Independent Parallel Reaction Model. The study focuses on the two active pyrolysis steps, the first one corresponds to the biomass components between 150 and 400 °C, with the decomposition peak between 300 and 350 °C, whereas the second corresponds to the plastic fraction with temperature ranging between 400 and 520 °C. The activation energy values obtained from the different kinetic methods for both steps are estimated at 240 and 250 kJ/mol, respectively. It was observed that the biomass components degradation obeys a third-order kinetic model, while the plastic fraction follows a first-order kinetic model. The analytical pyrolysis of the two main stages allows for the identification and semi-quantification of the compounds produced during municipal solid waste pyrolysis. Through analytical pyrolysis, it has been determined that up to 64 % of hydrocarbons are produced, of which 24 % correspond to aromatic compounds. Meanwhile, 20 % of oxygenated compounds were obtained, with ketones, furans, and acids being the most predominant families.