The thermal degradation behaviour and kinetic parameter of non-catalytic and catalytic pyrolysis of rice husk (RH) using rice hull ash (RHA) as catalyst were investigated using thermogravimetric analysis at four different heating rates of 10, 20, 50 and 100 K/min. Four different iso conversional kinetic models such as Kissinger, Friedman, Kissinger-Akahira-Sunose (KAS) and Ozawa-Flynn-Wall (OFW) were applied in this study to calculate the activation energy (EA) and pre-exponential value (A) of the system. The EA of non-catalytic and catalytic pyrolysis was found to be in the range of 152-190 kJ/mol and 146-153 kJ/mol, respectively. The results showed that the catalytic pyrolysis of RH had resulted in a lower EA as compared to non-catalytic pyrolysis of RH and other biomass in literature. Furthermore, the high Gibb's free energy obtained in RH implied that it has the potential to serve as a source of bioenergy production.
The impacts of low-transition-temperature mixtures (LTTMs) pretreatment on thermal decomposition and kinetics of empty fruit bunch (EFB) were investigated by thermogravimetric analysis. EFB was pretreated with the LTTMs under different duration of pretreatment which enabled various degrees of alteration to their structure. The TG-DTG curves showed that LTTMs pretreatment on EFB shifted the temperature and rate of decomposition to higher values. The EFB pretreated with sucrose and choline chloride-based LTTMs had attained the highest mass loss of volatile matter (78.69% and 75.71%) after 18 h of pretreatment. For monosodium glutamate-based LTTMs, the 24 h pretreated EFB had achieved the maximum mass loss (76.1%). Based on the Coats-Redfern integral method, the LTTMs pretreatment led to an increase in activation energy of the thermal decomposition of EFB from 80.00 to 82.82-94.80 kJ/mol. The activation energy was mainly affected by the demineralization and alteration in cellulose crystallinity after LTTMs pretreatment.
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.
The aim of this study was to understand the influence of catalyst in thermal degradation behavior of rice husk (RH) in catalytic fast pyrolysis (CFP) process. An iso-conversional Kissinger kinetic model was introduced into this study to understand the activation energy (EA), pre-exponential value (A), Enthalpy (ΔH), Entropy (ΔS) and Gibb's energy (ΔG) of non-catalytic fast pyrolysis (NCFP) and CFP of RH. The study revealed that the addition of natural zeolite catalyst enhanced the rate of devolatilization and decomposition of RH associated with lowest EA value (153.10 kJ/mol) compared to other NCFP and CFP using nickel catalyst. Lastly, an uncertainty estimation was applied on the best fit non-linear regression model (MNLR) to identify the explanatory variables. The finding showed that it had the highest probability to obtain 73.8-74.0% mass loss in CFP of rice husk using natural zeolite catalyst.
The aim of this study is to identify the optimum thermal conversion of Chlorella vulgaris with neuro-evolutionary approach. A Progressive Depth Swarm-Evolution (PDSE) neuro-evolutionary approach is proposed to model the Thermogravimetric analysis (TGA) data of catalytic thermal degradation of Chlorella vulgaris. Results showed that the proposed method can generate predictions which are more accurate compared to other conventional approaches (>90% lower in Root Mean Square Error (RMSE) and Mean Bias Error (MBE)). In addition, Simulated Annealing is proposed to determine the optimal operating conditions for microalgae conversion from multiple trained ANN. The predicted optimum conditions were reaction temperature of 900.0 °C, heating rate of 5.0 °C/min with the presence of HZSM-5 zeolite catalyst to obtain 88.3% of Chlorella vulgaris conversion.
The aim of this study was to pyrolyze individual (oil palm shell, empty fruit bunch and sawdust) as well as blend biomass in a thermogravimetric mass spectrometry (TG-MS) from room temperature to 800 °C at constant heating rate of 15 °C/min. The results showed that the onset TG temperature for blend biomass shifted slightly to lower values. Activation energy values were also found to decrease slightly after blending the biomass. Interestingly, the MS spectra of selected gases (H2O CH4, H2O, C2H2, C2H4 or CO, CH2O, CH3OH, HCl, C3H6, CO2, HCOOH, and C6H12) evolved from blend biomass showed decreased in the intensity as compared to their individual biomass. Overall, the blend biomass showed synergy which provides ways to expand the possibility of utilizing multiple feedstocks in one thermo-chemical system.
This study investigated on the co-pyrolysis of microalgae Chlorella vulgaris and high-density polyethylene (HDPE) waste mixtures which was performed with three types of catalysts, namely limestone (LS), HZSM-5 zeolite, and novel bi-functional LS/HZSM-5/LS. Kissinger-Kai (K-K) model-free method was coupled with Particle Swarm Optimization (PSO) model-fitting method using the thermogravimetric experimental data. A global sensitivity analysis was carried out using Latin Hypercube Sampling and rank transformation to assess the extent of impact of the input kinetic parameters on the output results. Furthermore, a thermodynamic analysis was performed to obtain parameters such as enthalpy change (ΔH), Gibb's free energy (ΔG), and entropy change (ΔS). The activation energy (EA) of the microalgae Chlorella vulgaris and HDPE binary mixture were found to be lower upon the addition of catalysts. Among the catalyst used, bi-functional LS/HZSM-5 catalyst exhibited the lowest EA (83.59 kJ/mol) and ΔH (78 kJ/mol) as compared to LS and HZSM-5 catalysts.
To valorize biomass waste, pyrolysis of orange peel was mainly investigated as a case study. In an effort to establish a more sustainable thermolytic platform for orange peel, this study particularly employed CO2 as reactive gas medium. Accordingly, this study laid great emphasis on elucidating the mechanistic role of CO2 in pyrolysis of orange peel. The thermo-gravimetric analysis (TGA) confirmed that no occurrence of the heterogeneous reactions between the solid sample and CO2. However, the gaseous effluents from pyrolysis of orange peel experimentally proved that CO2 effectively suppressed dehydrogenation of volatile matters (VMs) evolved from the thermolysis of orange peel by random bond scissions. Moreover, CO2 reacted VMs, thereby resulting in the formation of CO. Note that the formation of CO was being initiated at temperatures ≥550 °C. The two identified roles of CO2 led to the compositional modification of pyrolytic oil by means of lowering aromaticity.
Pyrolysis of agricultural biomass is a promising technique for producing renewable energy and effectively managing solid waste. In this study, groundnut shell (GNS) was processed at 500 °C in an inert gas atmosphere with a gas flow rate and a heating rate of 10 mL/min and 10 °C/min, respectively, in a custom-designed fluidized bed pyrolytic-reactor. Under optimal operating conditions, the GNS-derived pyrolytic-oil yield was 62.8 wt.%, with the corresponding biochar (19.5 wt.%) and biogas yields (17.7 wt.%). The GC-MS analysis of the GNS-based bio-oil confirmed the presence of (trifluoromethyl)pyridin-2-amine (18.814%), 2-Fluoroformyl-3,3,4,4-tetrafluoro-1,2-oxazetidine (16.23%), 5,7-dimethyl-1H-Indazole (11.613%), N-methyl-N-nitropropan-2-amine (6.5%) and butyl piperidino sulfone (5.668%) as major components, which are used as building blocks in the biofuel, pharmaceutical, and food industries. Furthermore, a 2 × 5 × 1 artificial neural network (ANN) architecture was developed to predict the decomposition behavior of GNS at heating rates of 5, 10, and 20 °C/min, while the thermodynamic and kinetic parameters were estimated using a non-isothermal model-free method. The Popescu method predicted activation energy (Ea) of GNS biomass ranging from 111 kJ/mol to 260 kJ/mol, with changes in enthalpy (ΔH), Gibbs-free energy (ΔG), and entropy (ΔS) ranging from 106 to 254 kJ/mol, 162-241 kJ/mol, and -0.0937 to 0.0598 kJ/mol/K, respectively. The extraction of high-quality precursors from GNS pyrolysis was demonstrated in this study, as well as the usefulness of the ANN technique for thermogravimetric analysis of biomass.
This study investigates the thermal decomposition, thermodynamic and kinetic behavior of rice-husk (R), sewage sludge (S) and their blends during co-pyrolysis using thermogravimetric analysis at a constant heating rate of 20 °C/min. Coats-Redfern integral method is applied to mass loss data by employing seventeen models of five major reaction mechanisms to calculate the kinetics and thermodynamic parameters. Two temperature regions: I (200-400 °C) and II (400-600 °C) are identified and best fitted with different models. Among all models, diffusion models show high activation energy with higher R2(0.99) of rice husk (66.27-82.77 kJ/mol), sewage sludge (52.01-68.01 kJ/mol) and subsequent blends (45.10-65.81 kJ/mol) for region I and for rice husk (7.31-25.84 kJ/mol), sewage sludge (1.85-16.23 kJ/mol) and blends (4.95-16.32 kJ/mol) for region II, respectively. Thermodynamic parameters are calculated using kinetics data to assess the co-pyrolysis process enthalpy, Gibbs-free energy, and change in entropy. Artificial neural network (ANN) models are developed and employed on co-pyrolysis thermal decomposition data to study the reaction mechanism by calculating Mean Absolute Error (MAE), Root Mean Square Error (RMSE) and coefficient of determination (R2). The co-pyrolysis results from a thermal behavior and kinetics perspective are promising and the process is viable to recover organic materials more efficiently.
Aquatic weeds pose hazards to aquatic ecosystems and particularly the aquatic environment in shellfish aquaculture due to its excessive growth covering entire freshwater bodies, leading to environmental pollution particularly eutrophication intensification, water quality depletion and aquatic organism fatality. In this study, pyrolysis of six aquatic weed types (wild and cultured species of Salvinia sp., Lemna sp. and Spirodella sp.) were investigated to evaluate its potential to reduce and convert the weeds into value-added chemicals. The aquatic weeds demonstrated high fixed carbon (8.7-47.3 wt%), volatile matter content (39.0-76.9 wt%), H/C ratio (1.5-2.0) and higher heating value (6.6-18.8 MJ/kg), representing desirable physicochemical properties for conversion into biofuels. Kinetic analysis via Coats-Redfern integral method obtained different orders for chemical reaction mechanisms (n = 1, 1.5, 2, 3), activation energy (55.94-209.41 kJ/mol) and pre-exponential factor (4.08 × 104-4.20 × 1017 s-1) at different reaction zones (zone 1: 150-268 °C, zone 2: 268-409 °C, zone 3: 409-600 °C). The results provide useful information for design and optimization of the pyrolysis reactor and establishment of the process condition to dispose this environmentally harmful species.
Metal, carbon and conducting polymer nanoparticles are blended with organic phase change materials (PCMs) to enhance the thermal conductivity, heat storage ability, thermal stability and optical property. However, the existing nanoparticle are expensive and need to be handle with high caution during operation as well during disposal owing to its toxicity. Subsequently handling of solid waste and the disposal of organic PCM after longevity usage are of utmost concern and are less exposed. Henceforth, the current research presents a new dimension of exploration by green synthesized nanoparticles from a thorny shrub of an invasive weed named Prosopis Juliflora (PJ) which is a agro based solid waste. Subsequently, the research is indented to decide the concentration of green synthesized nanoparticle for effective heat transfer rate of organic PCM (Tm = 35-40 °C & Hm = 145 J/g). Furthermore, an in-depth understanding on the kinetic and thermodynamic profile of degradation mechanism involved in disposal of PCM after usage via Coats and Redfern technique is exhibited. Engaging a two-step method, we fuse the green synthesized nanomaterial with PCM to obtain nanocomposite PCM. On experimental evaluation, thermal conductivity of the developed nanocomposite (PCM + PJ) increases by 63.8% (0.282 W/m⋅K to 0.462 W/m⋅K) with 0.8 wt% green synthesized nanomaterial owing to the uniform distribution of nanoparticle within PCM matrix thereby contributing to bridging thermal networks. Subsequently, PCM and PCM + PJ nanocomposites are tested using thermogravimetric analyzer at different heating rates (05 °C/min; 10 °C/min; 15 °C/min & 20 °C/min) to analyze the decomposition kinetic reaction. The kinetic and thermodynamic profile of degradation mechanism involved in disposal of PCM and its nanocomposite of PCM + PJ provides insight on thermal parameters to be considered on large scale operation and to understand the complex nature of the chemical reactions. Adopting thirteen different chemical mechanism model under Coats and Redfern method we determine the reaction mechanism; kinetic parameter like activation energy (Ea) & pre-exponential factor (A) and thermodynamic parameter like change in enthalpy (ΔH), change in Gibbs free energy (ΔG) and change in entropy (ΔS). Dispersion of PJ nanomaterial with PCM reduces Ea from 370.82 kJ/mol-1 to 342.54 kJ/mol-1 (7.7% reduction), as the developed nanomaterial is enriched in carbon element and exhibits a catalytic effect for breakdown reaction. Corresponding, value of ΔG for PCM and PCM + PJ sample within heating rates of 05-20 °C/min varies between 168.95 and 41.611 kJ/mol-1. The current research will unbolt new works with focus on exploring the pyrolysis behaviour of phase change materials and its nanocomposite used for energy storage applications. This work also provides insights on the disposal of PCM which is an organic solid waste. The thermo-kinetic profile will help to investigate and predict the optimum heating rate and temperature range for conversion of micro-scale pyrolysis to commercial scale process.
Driven by the need for solutions to address the global issue of waste accumulation from human activities and industries, this study investigates the thermal behaviors of empty fruit bunch (EFB), tyre waste (TW), and their blends during co-pyrolysis, exploring a potential method to convert waste into useable products. The kinetics mechanism and thermodynamics properties of EFB and TW co-pyrolysis were analysed through thermogravimetric analysis (TGA). The rate of mass loss for the blend of EFB:TW at a 1:3 mass ratio shows an increase of around 20% due to synergism. However, the blend's average activation energy is higher (298.64 kJ/mol) when compared with single feedstock pyrolysis (EFB = 257.29 kJ/mol and TW = 252.92 kJ/mol). The combination of EFB:TW at a 3:1 ratio does not result in synergistic effects on mass loss. However, a lower activation energy is reported, indicating the decomposition process can be initiated at a lower energy requirement. The reaction model that best describes the pyrolysis of EFB, TW and their blends can be categorised into the diffusion and power model categories. An equal mixture of EFB and TW was the preferred combination for co-management because of the synergistic effect, which significantly impacts the co-pyrolysis process. The mass loss rate experiences an inhibitive effect at an earlier stage (320 °C), followed by a promotional impact at the later stage (380 °C). The activation energy needed for a balanced mixture is the least compared to all tested feedstocks, even lower than the pyrolysis of a single feedstock. The study revealed the potential for increasing decomposition rates using lower energy input through the co-pyrolysis of both feedstocks. These findings evidenced that co-pyrolysis is a promising waste management and valorisation pathway to deal with overwhelming waste accumulation. Future works can be conducted at a larger scale to affirm the feasibility of EFB and TW co-management.
A comparative study of oxidative decomposition behavior of a wide range of vegetable oils and its correlation to iodine value (IV) using thermogravimetric analysis (TGA) was described. The oxidative decomposition of saturated fatty acids shows weight loss before 385 degrees C while oxidative decomposition of unsaturated fatty acids shows lower rate of weight loss (dWt/dt) compared to saturated fatty acids due to the oxidation process ('up taking ' of oxygen) involving breaking down of double bond to form primary and secondary oxidation products, which leads to some weight gain in the sample before being decomposed. The relative differences in the dWt/dt (%/min) of the both fatty acids give different decomposition steps in TGA thermogram, enabling IV to be determined through the percentage weight loss of saturated fatty acids per 100% of total sample weight (excluding weight loss from moisture and volatile compounds). Therefore, TGA method can be used as an alternative method for IV determination with no sample pre-dilution and solvent consumption. Using the TGA methods, good correlation (r = 0.9889) with standard AOCS method was achieved.
This study examined the combustion profile and kinetics of hydrochar produced from hydrothermal carbonisation (HTC) of Karanj fruit hulls (KFH). The HTC-KFH hydrochar combustion kinetics was investigated at 5, 10, and 20°C/min by thermogravimetric analysis. The kinetics model, Kissinger-Akahira-Sunose revealed the combustion kinetics parameters for the extent of conversion from 0.1 to 0.8; the activation energy varies from 114 to 67 kJ/mol respectively. The hydrochar combustion followed multi-steps kinetics; the Coats-Redfern models predicted the activation energies and pre-exponential constants for the hydrochar combustion zones. The diffusion models are the effective mechanism in the second and third zone.
Empty fruit bunches (EFBs), a waste material from the palm oil industry, were subjected to pyrolysis and gasification. A high content of volatiles (>82%) increased the reactivity of EFBs, and more than 90% decomposed at 700°C; however, a high content of moisture (>50%) and oxygen (>45%) resulted in a low calorific value. Thermogravimetric analysis demonstrated that the higher the heating rate and the smaller the particle size, the higher the peak and final reaction temperatures. The least squares estimation for a first-order reaction model was used to study the degradation kinetics. The values of activation energy increased from 61.14 to 73.76 and from 40.06 to 47.99kJ/mol when the EFB particle size increased from 0.3 to 1.0mm for holocellulose and lignin degradation stages, respectively. The fuel characteristics of EFB are comparable to those of other biomasses and EFB can be considered a good candidate for gasification.
The combustion characteristics of Karanj fruit hulls char (KFH-char) was investigated with thermogravimetry analysis (TGA). The TGA outlined the char combustion thermographs at a different heating rate and isoconversional methods expressed the combustion kinetics. The Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) methods authenticated the char average activation energy at 62.13 and 68.53kJ/mol respectively, enough to derive the char to burnout. However, the Coats-Redfern method verified the char combustion via complex multi-step mechanism; the second stage mechanism has 135kJ/mol average activation energy. The TGA thermographs and kinetic parameters revealed the adequacy of the KFH-char as fuel substrate than its precursor, Karanj fruit hulls (KFH).
In this study, dynamic vulcanization process was used to improve the thermal properties of calcium carbonate filled composites. The composites were prepared using a Z-blade mixer at 180oC and rotor speed 50rpm. Thermogravimetric analysis (TGA) and Differential scanning calorimetry (DSC) techniques were used to analyze the thermal properties of the composites. The vulcanized and unvulcanized PP/EPDM composites were filled by CaCO3 at 0, 10, 20, 30, and 40 %wt. Meanwhile, thermogravimetric analysis indicates that the total weight loss of PP/EPDM/CaCO3 composites decreased with increasing filler loading. Dynamic vulcanized composites have higher thermal stability, while the crystallinity of PP/EPDM/CaCO3 composites were increased as compared to unvulcanized composites. Therefore, the thermal properties were improved by the presence of
dynamic vulcanization process.
Cellulose acetate (CA) is an interesting material due to its wide spectrum of utilities across different domains ranging from absorbent to membrane filters. In this study, polystyrene (PS) nanofibres, and cellulose acetate/polystyrene (CA/PS) blend nanofibres with various ratios of CA: PS from 20: 80 to 80: 20 were fabricated by using electrospinning technique. The SEM images show that the nanofibres exhibited non-uniform and random orientation with the average fibre diameter in the range of 100 to 800 nm. It was found that the incorporation of PS had a great effect on the morphology of nanofibre. At high proportion of PS, no or less beaded CA/PS nanofibres were formed. Thermal properties of the composite nanofibres were investigated by using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques. The TGA results showed thermal stability of CA/PS nanofibres were higher than pristine CA.
In this research, a novel method was performed to obtain hydrogel with superior thermal stability by incorporation
of cellulose nanocrystals (CNC) into gelatin based hydrogel. Glutaraldehyde was used as cross-linker due to its high
chemical reactivity towards NH2
group on gelatin. Different ratio of gelatin/CNC hydrogel was produced in order to study
the effects of CNC towards the swelling behaviour and thermal stability of gelatin based hydrogel. The obtained hydrogel
was subjected to Fourier transform infrared (FTIR) to verify that gelatin had been cross-linked, swelling test with different
pH for swelling behaviour and thermogravimetric analysis (TGA) for thermal stability. The presence of C=N stretching
group in the FTIR spectrum for gelatin/CNC hydrogel indicated that the cross-linking reaction between gelatin monomer
had been successfully carried out. The hydrogel showed impressive pH sensitivity and maximum swelling was obtained
at pH3. The TGA results clearly showed that the incorporation of CNC into gelatin was able to produce hydrogel with
higher thermal stability compare to neat gelatin.