Activation Energy Of Pyrolysis Research Articles

A multi-step kinetics study on Chang-7 shale pyrolysis: Impact of shale inherent minerals

Pyrolysis is a significant process for the in-situ conversion and aboveground retorting of oil shale. However, the impact of inherent minerals on shale pyrolysis is still unclear. This study analyzed the effect of different inherent minerals on pyrolysis of Chang-7 oil shale, which is noted for its low carbonate, high silicate, and high pyrite content, through an integrated evaluation of kinetic and thermodynamic parameters. The pyrolysis process, arranged from 350℃ to 600℃, was deconvoluted into three distinct processes—bitumen, kerogen, and pyrite pyrolysis—using the bi-Gaussian method. Thermodynamic results showed that pyrolysis was endothermic and non-spontaneous. Minerals significantly reduced the pyrolysis activation energy. The ratio of pyrolysis activation energies for shale to kerogen increased with the carbonate-to-silicate content ratio. Master plot analysis indicated that, mineral removal shifted the reaction model from the contraction geometry model (Rn) to the diffusion model (Dn). This transition in reaction model was due to the formation of pores from demineralization and organic decomposition, facilitating the diffusion of heat and activated molecules into the interior of particles, which has been confirmed by porosity determination. This work provides an in-depth understanding of the impact of inherent minerals on shale pyrolysis, which is conducive to the efficient development and utilization of oil shale resources.

The exploration of effect for nano-Al2O3 on solid waste based superfine tailings cemented paste backfill: Pyrolysis property, hydration mechanism and environmental risk

Resource utilization of superfine tailings has become a key research direction in filling mining. This study analyzes the mechanical properties, pyrolysis mechanism and hydration mechanism of nano-Al2O3(NA)-doped solid waste based superfine tailings cemented paste backfill (SWSCPB) by multiple microscopic characterization methods and pyrolysis kinetic theory. The results show that the main temperature interval for the pyrolysis of SWSCPB to happen is 280–900 °C, which is divided into two stages of dehydroxylation and decarbonization. The apparent activation energy(E) and pre-index factor(A) of pyrolysis are higher than those of NA0 and NA2 at 1 % NA dosage, indicating that NA increases the energy barrier of pyrolysis, the percentage of activated molecules, and the collision probability of hydration products in SWSCPB, but decreases due to agglomeration at exceeds 1 % NA dosage. NA can enhance macroscopic strength of SWSCPB, with the highest strength at 1 % NA dosage. Compared with NA0 and NA2, more hydration products such as AFt and C-(A)-S-H are present in NA1, and the distribution of Q2 and Q4 in C-(A)-S-H is more pronounced, with a higher degree of polymerization, a stronger tendency for the conversion of non-bridging to bridging oxygen bonds, and fewer pores in the microstructure of SWSCPB. The NA dosage can provide more nuclei for the formation of AFt, C-(A)-S-H in SWSCPB, and can also promote the replacement of Si by Al for the conversion of C-S-H to C-(A)-S-H with higher polymerization. In addition, the leaching risk and mechanism of heavy metal ions from SWSCPB are preliminarily explored in combination with leaching experiments. The results provide new insights and guidance for the application of SWSCPB in filling mining under cleaner production targets.

Kinetics study of pyrolysis of petroleum sludge and characterization of char

Thermochemical conversion (or pyrolysis) has emerged as an effective technique for the disposal of sludge generated in process industries. This paper reports physicochemical characterization and kinetic analysis of pyrolysis of sludge from a petroleum refinery and characterization of resultant char. The sludge had high volatile matter (>70 wt%) and low ash content (15 wt%). Pyrolysis of sludge was studied using a thermo-gravimetric analyzer (TGA). The TGA data was analyzed using two isoconversional models, viz. KAS and Vyazovkin AIC are used for the deduction of kinetic triplets, viz. activation energy, pre-exponential factor, and reaction mechanism. The activation energy (Ea ) of sludge pyrolysis varied in the 64.79–190.37 kJ/mol range. The pre-exponential factor varied from 1.18E + 07 to 4.29E + 12 s−1. The predominant solid-state mechanism of thermal conversion was an order-based reaction (F2/F3). The thermodynamic factors (viz. ΔH, ΔS, ΔG) of sludge pyrolysis were also determined. Relatively small values of (Ea – ΔH) ∼ 5 kJ/mol revealed high susceptibility of sludge for thermal conversion. Residual char after pyrolysis was characterized for physicochemical properties. The char properties were fixed carbon = 54.37%, calorific value = 22.48 MJ/kg, and BET surface area = 18.35 m2/g. These properties make char suitable for numerous applications.

Study on molten salt on torrefaction and subsequent pyrolysis of elm branches

Torrefaction was a promising pretreatment for enhancing biomass properties, and molten salt torrefaction could achieve superior torrefaction benefits at equivalent temperatures. To explore the difference between molten salt torrefaction (MT) and conventional torrefaction (CT) and the effect of which on the subsequent pyrolysis of biomass, torrefaction experiments at 260 ℃ and pyrolysis experiments were conducted in a horizontal furnace, a thermogravimetric mass spectrometry (TG-MS) and a pyrolysis gas-chromatography mass-spectrometry (Py-GC-MS), respectively. The results showed that the O/C of washed MT sample (MTw) decreased by 13.89 % and the volatile content decreased by 14.56 % compared with washed CT sample (CTw). Concurrently, the MTw sample demonstrated the highest calorific value and largest specific surface area among the samples. The maximum weight loss rate of MT sample during subsequent pyrolysis increased. In comparison with CT, MT could decrease the pyrolysis activation energy. Furthermore, MTw sample produced more H2 and CH4, while simultaneously less CO2 and CO during pyrolysis compared with CTw. The bio-oil derived from the MTw sample exhibited the lowest relative content of acidic compounds and the highest relative content of aromatic compounds, signifying its enhanced quality.

Kinetic characteristics and product distribution of tar-rich coal in-situ underground pyrolysis: Influence of heterogeneous coal seam

Tar-rich coal contains more hydrogen-rich structures such as aliphatic side chains and bridge bonds, which is a good raw material for coal to oil. In-situ underground pyrolysis of tar-rich coal has significant advantages such as environmental friendliness and high safety factor; it is an efficient, clean coal utilization technology. Due to the influence of geological structure and other factors in the formation process, underground coal seam was often heterogeneous, generally accompanied by coal gangue interlayers. Due to the coal gangue being relatively dense and has poor thermal conductivity, it is also rich in metal oxides, it would inevitably affect the pyrolysis characteristics and product distribution during the pyrolysis process of heterogeneous tar-rich coal seam. The pyrolysis characteristics of heterogeneous tar-rich coal seam with different positions and layers of coal gangue interlayer were investigated by the thermogravimetric analyzer, and related kinetic parameters were obtained by the distributed activation energy model (DAEM). Based on the fixed bed tube furnace reactor, the pyrolysis experiments of heterogeneous tar-rich coal seam with different positions and layers of coal gangue interlayer were also carried out, and the pyrolysis products were characterized and analyzed. The thermogravimetric results showed that in the pyrolysis process of heterogeneous tar-rich coal seam, the initial pyrolysis temperature and the temperature corresponding to the maximum weight loss rate shifted to the higher temperature range, and the pyrolysis characteristic index decreased significantly. Under the same conditions, the corresponding pyrolysis characteristic indexes of the upper coal gangue interlayer and 4 layers of coal gangue interlayer were lower, which were 11.69 (10−8·%·min−1·℃−3) and 11.65 (10−8·%·min−1·℃−3), respectively. Compared with homogeneous tar-rich coal seam, pyrolysis activation energies of heterogeneous coal seam generally showed the decreasing trend. Under the conditions of the upper part containing coal gangue interlayer and the upper-and-lower parts containing coal gangue interlayer, the pyrolysis activation energies were higher due to the hindrance of the cover layer of coal gangue to the volatile release, which were 555.88 kJ·mol−1 and 546.66 kJ·mol−1 respectively. The results of fixed bed pyrolysis experiments showed that compared with homogeneous tar-rich coal seam, the tar yield obtained was reduced, the degree of tar lightening was significantly improved, and the proportion of lighter tar was up to 70.00 wt%. The contents of aromatic hydrocarbons and phenolic compounds in tar increased, the contents of aliphatic hydrocarbons and oxygenated compounds decreased significantly, and the maximum reductions were nearly 4.50 wt% and 6.50 wt%, respectively. The gas yield increased, the proportions of H2 and CO2 in the gas increased, and the proportions of CO and CH4 decreased to varying degrees. The tar yields were lower under the conditions of upper gangue and 4 layers gangue, which were 6.53 wt% and 5.81 wt%, respectively, and the degrees of tar lightening were also more significant. From the relationship between pyrolysis characteristic parameters and tar properties of heterogeneous tar-rich coal seam pyrolysis, it was found that the existence of coal gangue interlayer was not conducive to the tar production, but it could promote the lightening of tar and improve the tar quality. Exploring the kinetic characteristics and pyrolysis product distribution of heterogeneous tar-rich coal seam could provide theoretical guidance for the site selection of in-situ underground pyrolysis engineering and the well arrangement.

A comparative study on the slow pyrolysis of Miscanthus (Miscanthus×giganteus Greef et Deu.) cultivated on agricultural and contaminated soils: Assessment of distribution of final products

This study aims to investigate the slow pyrolysis behavior of uncontaminated (MSC-I - reference) and heavy metals contaminated (MSC-R) samples with heavy metals from the tailings of a Pb-Zn-Cu flotation mine, consisting of whole stems of Miscanthus. Physicochemical properties of raw materials were investigated through instrumental characterization techniques (Atomic Absorption Spectrometry (AAS), Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy, and X-ray diffraction (XRD)), while the pyrolysis process was monitored by simultaneous thermal analysis techniques (thermogravimetry (TG) – derivative thermogravimetry (DTG)), coupled with Mass spectrometry (MS), for evolved gas analysis. After determination of the lignocellulose content (cellulose, hemicellulose, and lignin) and extractive of the MSC-I and MSC-R samples, it was found that Pb, Zn, Fe, and Mn in MSC-R lead to very fast decomposition of extractive fraction, which facilitates their distribution in formed bio-char, together with lignin char-participation, acting catalytically. It was established that a much greater fraction of extractives decomposition products and non-volatile heavy metals are incorporated in MSC-R bio-char increasing its yield (23 %), compared to MSC-I bio-char yield (21.5 %). It was identified that MSC-R has increased production of H2, CO, and CO2, while decreased production of CH4, influenced by Fe (Fe has a significant positive effect on CO2 evaluation during MSC-R pyrolysis, enhancing decarboxylation process). It was established that CH4 reforming reactions catalyzed by iron additionally affect methane reduction, and increase production of H2, compared to the reference sample. Isoconversional kinetic analysis showed that pyrolysis reactions profile was strongly conditioned by the presence of heavy metals, such as Cd, Pb, and Zn, because they affect the modification of biomass lignocellulosic structure. Also, it was found that small amounts of Cd present in MSC-R can increase pyrolysis activation energy of three pseudo-components, and inhibit their deoxygenation, thus increasing yield of bio-char.

Study on the properties and components of solid-liquid products by co-pyrolysis of sludge and cotton stalk

The effects of sludge content and pyrolysis temperature on the pyrolysis process and product properties were studied through the co-pyrolysis of sludge and cotton stalk. Multi-objective fuzzy hierarchical analysis was used to analyze the multiphase properties of pyrolysis products, and describe the internal relationship between pyrolysis conditions and product properties. It has been proved using kinetic calculation that the mass ratio of sludge and cotton stalk is higher than 1:2 required the lower pyrolysis activation energy. According to the comparison between experimental and theoretical results, the addition of sludge is beneficial to increase the bio-oil yield. In terms of product performance, the addition of sludge and increase of pyrolysis temperature both can improve the specific surface area, pore volume of biochar and the pH value of bio-oil, reduce the total acid content, increase the total phenol content and optimize calorific value of bio-oil. The specific surface area of biochar, calorific value of bio-oil, total phenol content and pH were evaluated by multi-objective decision analysis method, the optimum process condition of sludge: cotton stalk = 2:1 at 600 ℃. Under the conditions, the specific surface area of biochar is 57.40 m2/g, the pH of the bio-oil is 8.06, the total acid content is 5.94 mg/g, the calorific value is 27.18 KJ/g and the total phenol content is 47.32 mg/g, respectively. Compared to the pyrolysis product of cotton stalks, the specific surface area is increased almost 20 times, the calorific value is increased by 13 %, the total acid content is decreased by 95 %, and the total phenol content is similar. This study proposed a preparation process of bio-oil with high performance, and provided a theoretical basis for the subsequent co-pyrolysis research.

Thermal conversion studies of lignin pyrolysis and the catalytic effect of fe: A reactive molecular dynamics study

Lignin is one of the important components of biomass, and its pyrolysis process has been widely studied. The advantages of iron-based catalysts are their low cost, low environmental pollution, and the ability to extract and reuse from the system. However, research on the effect of metallic iron on lignin pyrolysis is limited. This study revealed the influence of iron on lignin pyrolysis process at the microscopic level through reactive molecular dynamics (ReaxFF MD) simulation, while considering the influence of different temperatures. It was found that increasing the temperature can increase the production of H2 and CO gases and improve the efficiency of lignin decomposition. In addition, the addition of catalyst iron can accelerate the decomposition of the benzene ring, making the lignin pyrolysis process deeper and more thorough, while increasing the production of H2 and CO. The activation energy of the system was calculated and it was found that the addition of catalyst iron can significantly reduce the activation energy of lignin pyrolysis, proving the excellent catalytic effect of the catalyst. The catalytic pyrolysis strategy provided in this study, using iron as a catalyst to catalyze the pyrolysis process of lignin, can effectively utilize biomass resources in industrial production.

Kinetic Properties of Combustion and Pyrolysis of Masson Pine with Synergistic Flame Retardancy by GUP-APP-silica Sol

ABSTRACT In order to investigate the effect of guanylurea phosphate-ammonium polyphosphate-silica sol on the combustion and pyrolysis characteristics of Masson Pine, UL-94 horizontal and vertical burner, LOI tester, cone calorimeter, and thermogravimetric analysis were used to study the flame retardant wood, and Coats-Redfern model was used to analyze its pyrolysis kinetics. The results showed that the combined use of guanylurea phosphate-ammonium polyphosphate-silica sol had a significant synergic flame retardant effect on Masson pine. When the mass ratio of guanylurea phosphate, ammonium polyphosphate, and silica sol was 2:1:1, the heat release rate and total heat release of flame retardant pine were decreased by 54.7% and 44.7% compared with pure Masson pine, and the LOI was increased by 77.8% compared with the control group. In addition, the addition of silica sol in the flame retardant reduces the effect of flame retardant on the mechanical properties of wood. Raman analysis of carbon layer showed that the R-value of char residue decreased by 5% and 13% when the mass fraction ratio of guanylurea phosphate, ammonium polyphosphate, and silica sol was 5:1:2 and 2:1:1, respectively, indicating that the compound flame retardant effectively promoted the conversion of amorphous carbon into graphite structure. The TG results of the 5:1:2 and 2:1:1 ratios of guanylurea phosphate, ammonium polyphosphate, and silica sol groups showed that the pyrolysis temperature of flame-retardant pine advanced by about 100°C at the heating rate of 15 ℃/min, and the final char residue rate and apparent activation energy were 15.22%, 18.61%, 24.35 kJ/mol, and 23.76 kJ/mol, respectively. These results indicated that the synergistic flame retardant system of guanylurea phosphate-ammonium polyphosphate-silica sol reduced the apparent activation energy of pine pyrolysis, effectively inhibited the pyrolysis of Masson Pine, and enhanced the thermal stability, char forming ability, and flame retardant property.

Pyrolysis kinetics of waste ryegrass under nitrogen and air atmosphere

To investigate the pyrolysis reaction of ryegrass, we conducted a simultaneous thermal analysis using thermogravimetric(TG) analyzers. This involved obtaining data through Thermogravimetry (TG), Derivative Thermogravimetry (DTG), and Differential thermal analysis (DTA) techniques. The experiments were conducted under dynamic nitrogen and air atmospheres at different heating rates. The kinetic parameters of ryegrass pyrolysis were determined using the Kissinger method, the Flynn-Wall-Ozawa (FWO) peak conversion rate approximate equivalence method, the Flynn-Wall-Ozawa (FWO) equal conversion rate method, and the Škvára-Šesták (S–S) method. It provides a theoretical basis for the reuse of ryegrass resources. The findings indicated that the pyrolysis temperature of ryegrass increased with the accelerated rate of temperature increase in both atmospheres. The average weight loss rate of pyrolysis of ryegrass in the air atmosphere (92.27 %) is higher than that compared to that in a nitrogen atmosphere (86.11 %). Additionally, the temperature required for complete decomposition is lower in the former case. The FWO peak conversion rate approximation equivalence approach and the FWO equal conversion rate method do not apply to the solution of the pyrolysis activation energy of ryegrass. The pyrolysis activation energy for the two decomposition stages, as calculated by the Kissinger method, is 165.73 and 185.86 kJ/mol−1 in the air atmosphere, and 219.99 and 277.02 kJ/mol−1 in a nitrogen atmosphere, respectively. The activation energy and mechanism function of ryegrass pyrolysis calculated by using the S–S method are as follows: [−ln(1−α)]2, 119.79, 104.31, 95.75, and 91.93 kJ/mol−1 in air atmosphere, (1−α)−1, 176.64, 67.89, 61.15, and 54.25 kJ/mol−1 in nitrogen atmosphere, respectively. The activation energy of ryegrass pyrolysis, as determined by both the Kissinger method and S–S method, was found to be higher under an air atmosphere compared to a nitrogen atmosphere.

Thermal behavior analysis and biochar formation through co-pyrolysis of de-oiled microalgae biomass and wood sawdust for ecofriendly resource utilization

The co-pyrolysis of biomass wastes is of great importance for the integration of waste management and renewable energy sources, and the achievement of sustainable development goals. In this context, this study aimed to understand the reaction mechanisms and their behavior by examining the co-pyrolysis reactions of de-oiled microalgae and wood sawdust wastes. In this scope, the co-pyrolytic behavior of wood sawdust – de-oiled microalgae blends was determined by the thermogravimetric method, and co-pyrolysis kinetics and thermodynamics were calculated using model-free methods. In addition, biochar was produced from these blends under the conditions of 600 °C temperature and 20 °C min−1 heating rate, and the characterization of biochars was performed. According to the obtained results, it was observed that the degradation time of de-oiled microalgae was longer than that of wood sawdust, depending on the complexity of its structure. The main decomposition of wood sawdust occurred in a single step within the temperature range of approximately 200–400 °C, whereas the main decomposition of de-oiled microalgae occurred in multiple steps within the temperature range of approximately 200–550 °C. The calculated pyrolysis activation energy values for the biomasses ranged from approximately 149 to 180 kJ mol−1, while for the blends, these values ranged from approximately 159 to 203 kJ mol−1. Additionally, the higher HHV values of the biochars produced from the blends (approximately 10 MJ kg−1 higher than the others) increased their potential as a fuel. Based on these results, biochars produced via co-pyrolysis can be considered as a suitable option to be used as a fuel in terms of energy efficiency.

Pyrolysis of metal oxides treated Canarium schweinfurthii Shell: Investigation of thermogravimetric kinetics and thermodynamics

Metal oxides as catalysts alter the properties of the pyrolysis vapor secondary reactions during the thermal decomposition of several biomass leading to high-value bio-oils. This study aimed to investigate the thermal decomposition characteristics of Canarium Schweinfurthii (CS) shells that were treated with various metal oxides (ZnO, CuO, Fe2O3/FeO, and Fe2O3) using pyrolysis. The study also sought to identify pyrolysis reaction parameters (kinetics and thermodynamics parameters) that are not widely documented. Thermogravimetric pyrolysis was carried out at different heating rates, and the undocumented pyrolysis kinetic parameters were determined using the Flynn-Wall Ozawa method (FWO) according to American Standard Testing and Materials (ASTM) 6441 guidelines for assessing biomass decomposition. The metal oxide-treated CS shells lost significant weight between 62 and 67 wt% during the thermogravimetric pyrolysis, lower than 75 wt% of the CS shell. The average activation energies (Eα) for pyrolysis of the ZnO, CuO, Fe2O3/FeO, and Fe2O3 treated CS shells were 203.04, 155.35, 338.85, and 219.92 kJ/mol, respectively in contrast to that of the untreated CS-shell. The Bayesian Information Criteria revealed that the diffusion kinetics of the Gistling-Brounshtein model best describes the pyrolysis of the shell mixed with metal oxides. The metal oxides affected the CS shells' pyrolysis kinetic parameter (Eα), which can promote pyrolysis vapor upgrading to encourage the widespread use of metal oxides in pyrolysis for bioenergy and chemical recovery.

Experimental and theoretical study on the smoldering combustion of size-fractioned forest duff particles

Smoldering combustion process has been suggested as a new method potentially useful in the treatment of biosolids. Natural forest duff (FD) often consists of organic fuel layers with varying particle sizes, yet the influence of the size-fractioned particles on the smoldering combustion dynamics in terms of the heat and mass transfer is not well understood. In this study, the oxidative pyrolysis and smoldering behavior of FD samples with four particle sizes (0 < d1 ≤ 0.425 mm, 0.425 < d2 ≤ 1 mm, 1 < d3 ≤ 2 mm, 2 < d4 ≤ 4 mm) were experimentally and theoretically investigated. Micro-scale thermo-gravimetric (TG) analysis, and a four-step kinetic model incorporating water evaporation, FD pyrolysis, FD oxidation and char oxidation showed that the activation energy of the FD pyrolysis and the ash content are negatively correlated, while the activation energy of the char oxidation increases from 87.26 kJ mol−1 to 119.22 kJ mol−1 with the particle size increasing from d1 to d4. Furthermore, the order of the combustion performance of the FD samples is shown as d1<d2<d4<d3. A series of laboratory-scale smoldering experiments revealed that the peak smoldering temperature increases with the fuel depth while the horizontal spread rate decreases with the fuel depth. Both the peak mass loss rate and the smoldering duration presented a reverse order (d1>d2>d4>d3) of the combustion performance found in the TG tests. A simplified heat transfer analysis qualitatively revealed the beneficial effects of the size-fractioned particles on the smoldering spread rate, while a mass transfer analysis revealed the favorable and adverse influences of the particle size on the kinetic-controlled and diffusion-controlled char oxidation rate, respectively. These findings verify that particle sizes alter the FD physicochemical properties (e.g., specific surface area, bulk density, porosity, permeability, chemical components, and lower calorific value), which in return impact the chemical kinetics, heat and mass transfer process in smoldering combustion. This work provides new insights into the effects of the size-fractioned particles on smoldering combustion, ultimately improving the fundamental understanding for optimizing particle sizes for energy conversion and usage.

Investigation on pyrolysis characteristics and kinetics of sewage sludge with different heat-mass transfer rates

The pyrolysis process of sewage sludge (SS) in fluidized bed has the characteristics of high speed heat-mass transfer rate, which challenges the reliability of thermal analysis methods. In this study, TGA and fast-reaction thermogravimetric analysis (FR-TGA) were used to investigate the pyrolysis characteristics of SS. The apparent kinetic parameters of pyrolysis at constant heating rate (β) and excellent heat-mass transfer rate were obtained, respectively. Resuls shows that, the pyrolysis of SS under both conditions showed multi-step reaction characteristics. The apparent activation energy (Eα) of pyrolysis of SS determined by FR-TGA was significantly lower than that determined by TGA. With the increase in temperature of the FR-TGA reactor, E decreased further. The excellent heat-mass transfer rate could improve the reactivity during SS pyrolysis. In addition, FR-TGA experiments showed that moisture could promote the pyrolysis of organic components in SS and further reduce Eα. Based on these conclusions, a kinetic model of SS pyrolysis under excellent heat-mass transfer rate was established. This study can serve as a reference for predicting the pyrolysis behavior of SS in a fluidized bed reactor.

Polyethylene deflagration characterization and kinetic mechanism analysis

In this paper, the combustion process of polyethylene (C100H202) was simulated by experiment and Reaction Force Field molecular dynamics (ReaxFF MD) simulation, and the influence of density and temperature on the deflation of C100H202 was investigated. The flame propagation characteristics of C100H202 with different concentrations were studied by the Hartmann experiment system, and the pyrolysis characteristics of C100H202 under N2 and O2 atmospheres were studied by the TG test. The pyrolysis activation energy of C100H202 in N2 and O2 atmospheres is 72.160 kJ/mol and 92.356 kJ/mol, respectively, which is consistent with the reaction activation energy of 97.110 kJ/mol calculated by simulation. In addition, it is found through simulation that the increase in system density will increase the generation and consumption of intermediate products such as C2H4, which explains the phenomenon of more intense detonation when the concentration of C100H202 increases from 0.0002 g/cm3 to 0.0005 g/cm3 in dust ignition experiment from the molecular level. The results show that physical methods such as cooling down and releasing inert gas and chemical methods that consume functional groups have significant effects on the inhibition of hydrocarbon deflagrations from a microscopic point of view, and provide theoretical support for the study of the inhibition of hydrocarbon deflagrations.

Co-pyrolysis of chrome-tanned leather shavings with wheat straw: Thermal behavior, kinetics and pyrolysis products

The thermal behavior and kinetics of chrome-tanned leather shavings (CLS)/wheat straw (WS) blends at different mass ratios during co-pyrolysis were investigated, and the pyrolysis products were characterized. Model-free isoconversional and master-plots methods were applied to determine kinetic triplet of the pyrolysis/co-pyrolysis of CLS, WS and their blends based on thermogravimetric (TG) analysis. Results showed that the activation energy for CLS pyrolysis was reduced by the addition of WS, and a synergistic promoting effect predominated across the majority of temperature ranges and feedstock compositions during the co-pyrolysis process. TG-Fourier transform infrared spectrometry-Mass spectrometry analysis showed the changes in evolution profiles of H2O, CO, CO2, HNCO and pyrrole during pyrolysis. The pyrolysis solid residues were characterized and results indicated that the addition of WS to CLS can increase solid residue yield and potentially inhibit the formation of hexavalent chromium during pyrolysis. This study helps to foster a promising solution for the valorization and safe disposal of chromium-containing solid wastes from leather industry.

Chemical insight into thermal degradation, chemical kinetics, and thermodynamics behavior of sewage sludge through thermogravimetry and Fourier transform infrared analysis

Pyrolysis emerges as a promising path for sewage sludge (SS) management and value creation by producing compounds with enhanced utility. This study focuses on a comprehensive analysis of the thermal decomposition of SS using thermogravimetric analysis (TGA) and Fourier transform infrared spectrometry (FTIR). The TGA and FTIR were employed to evaluate the pyrolysis behavior, kinetics, and characteristics during pyrolysis of SS. The process revealed three distinct stages: 1st stage ranged between 30–185 °C with the removal of moisture, 2nd stage saw devolatilization of SS in the range of 185–595 °C, and the 3rd stage was mainly the formation of char in the temperature range of 595–900 °C. Pyrolysis kinetics, reaction mechanisms, and thermodynamic properties were extensively investigated at three different heating rates of 10, 20, and 30 °C /min. It was observed that with the temperature rise, the decomposition rate also increased rapidly, notably for the heating rate of 30 °C/min. Using Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose, Starink, and Tang methods, activation energies for SS pyrolysis were estimated for α in the range of 0.2–0.85, and the average value for that range was found to be 84.72, 92.29, 91.99, and 91.76 kJ/mol, respectively for different iso-conversional methods. The chemical kinetics analysis through Coats-Redfern methods identified that 3-D diffusion-reaction mechanisms have the highest coefficient of determination among the other models. Criado z-master plot emphasizes the prevalence of Avrami-Erofeev (A4) as the bestsuited reaction model in combination with α, providing a detailed examination that illuminates the complex processes and mechanisms inherent in the pyrolysis of sewage sludge.

Pyrolysis characteristics and kinetic investigation of waste groundnut shells using thermogravimetric analyzer, Py-FTIR, and Py-GC-MS

The objective of the present study was to investigate the bioenergy and resource recovery potential of groundnut shells (GNS) through pyrolysis. The release of vapours at short time scales and their composition were investigated using analytical pyrolysis coupled with Fourier transform infrared (FTIR) spectroscopy and gas chromatography/mass spectrometry (GC/MS). The thermal decomposition behaviour and kinetic evaluation were carried out using a thermogravimetric analyzer (TGA). Five iso-conversional models and master plots method were utilized to explore the kinetic parameters and reaction mechanism at dynamic heating rates (10, 20, and 30 °C min−1). X-ray fluorescence spectroscopy (XRF) was employed to detect the ash composition, which is essential to evaluate the slagging and fouling potential of the biomass when used for bioenergy. TG data revealed three distinct stages of decomposition, while an immense amount of biomass disruption was observed at a higher heating rate (30 °C min−1). Further, the average apparent activation energy of pyrolysis determined using KAS, ST, DAEM, and VZ were 223.26, 214.57, 207.97, and 117.24 kJ mol−1, respectively. The extreme emission of carbon dioxide and carbonyl compounds was discovered through Py-FTIR. The increased formation of hydrocarbons (14.22–34.26%), alcohols (1.41–9.43%), and reduction in phenols (19.13–18.67%) at different temperatures (450, 550, and 650 °C) were validated by Py-GC-MS. Overall, the findings demonstrate that GNS is a promising feedstock for pyrolysis to produce valuable fuel molecules and chemicals.

Different effects of mesophilic and thermophilic anaerobic digestion on subsequent pyrolysis: Characteristics, kinetics and thermodynamic analysis

Anaerobic digestion (AD) combined with pyrolysis has been used as an innovative sludge-to-energy process that enhances energy recovery. This study investigated the different impacts of mesophilic and thermophilic AD on subsequent pyrolysis. The pyrolysis characteristics, kinetics, and thermodynamics of raw sludge (RS) and digested sludge (DS) after both mesophilic and thermophilic AD were investigated using thermogravimetric analysis (TGA) and three kinetic models (Starink, Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose). TGA results indicated that thermophilic AD reduced the weight loss from 71.2-75.6 % for RS to 55.0–59.1 % for DS, more considerably than mesophilic AD (reducing from 70.6-75.2 % to 61.3–69.5 %), indicating higher organic matter removal. Kinetic analysis showed that the activation energy (E) of RS and DS pyrolysis ranged from 128.9 to 399.9 kJ/mol and 117.3 to 470.4 kJ/mol, respectively. Mesophilic AD generally increased the E, while thermophilic AD did not markedly alter E at low conversion rates (0.2–0.5) but increased it at high conversion rates (0.6–0.8), changing from 203.7–399.9 kJ/mol for RS to 248.9–470.4 kJ/mol for DS. Thermodynamic analysis showed that mesophilic AD generally enhanced pyrolysis favorability and reactivity but impeded activated complex formation. Thermophilic AD enhanced favorability and favored complex formation at low conversion rates but hindered it at high conversion rates. Reactivity varied with thermophilic AD extent, with excessive AD reducing reactivity. Pyrolysis–gas chromatography/mass spectrometry analysis confirmed that AD, on the one hand, decomposed biodegradable organics into low-molecular-weight organics, retained them in the DS, and facilitated subsequent pyrolysis. On the other hand, AD could accumulate large bio-refractory molecules, rendering DS less prone to pyrolytic decomposition. This effect of thermophilic AD was more significant than that of mesophilic AD. Given more favorable change was observed in kinetics and thermodynamics at lower conversion rates, low-temperature pyrolysis to produce biochar might be a promising strategy for DS treatment. The insights gained in this study may guide the optimization of AD conditions to maximize the efficiency of subsequent pyrolysis, providing more insight into the thermochemical conversion of DS and pyrolysis design.

Effect of severe torrefaction by superheated steam on pinewood pyrolysis kinetics and pyrolytic oil compounds

Hemicellulose, cellulose, lignin and extractives generally contribute a variety of compounds to pyrolytic oil during pyrolysis. Severe torrefaction process to remove those compounds may influence the diversity and quality of pyrolytic oil. In this study, pinewood, as a frequently studied biomass for pyrolysis research, was firstly torrefied by superheated steam (SHS) in different intensities prior to both slow pyrolysis and Py-GCMS. The kinetic study demonstrated that the activation energy of pyrolysis for the biomass increased greatly from 172.66 kJ mol−1 to a maximum of 400.18 kJ mol−1 after SHS torrefaction. The pyrolytic oil from both slow pyrolysis and Py-GCMS were analyzed. The content of hemicellulose and cellulose biomass reduced with increasing SHS torrefaction intensities. As a result, the light oxygenates, sugars and furans in pyrolytic oil decreased greatly, whereas the concentration of phenol and aromatics improved. In addition, the phenolic compounds shifted to smaller molecular weight and the acetic acid as an adverse factor in pyrolytic oil decreased and even disappeared under severe torrefaction. SHS torrefaction provide a new insight for biomass pretreatment for further pyrolysis.