Distributed Activation Energy Model Research Articles

Systematical analysis and application of distributed activation energy model (DAEM) with Weibull distribution for pyrolysis kinetics of lignocellulosic biomass

The distributed activation energy model (DAEM) is a comprehensive and accurate kinetic model for describing the thermal decomposition kinetics of complex materials. The Gaussian distribution is commonly used for representing the activation energy distribution, however, it is symmetric and cannot reflect the reactivity asymmetry involved in complex chemical kinetics. The Weibull distribution offers an alternative to represent the distribution of activation energies. This study performed a systematical investigation of the DAEM with Weibull distribution, focusing particularly on its asymmetric characteristics. Additionally, the DAEM with Weibull distribution was applied to analyze the pyrolysis kinetics of rice straw and cotton stalk. The theoretical analysis results showed that the DAEM with Weibull distribution could provide abundant flexibility to elucidate the asymmetric reactivity of complex chemical kinetics. The pyrolysis processes of rice straw and cotton stalk could be deconvoluted into several sub-processes, which could be accurately described by the DAEMs with Weibull distribution. The obtained Weibull distributions of activation energies for those deconvoluted sub-processes validated their asymmetric reactivities. It is expected that the results could help in exploring the kinetic mechanisms of lignocellulosic biomass pyrolysis and facilitate the application of the DAEM with Weibull distribution in analyzing complex chemical kinetics.

Elucidating Kinetic Mechanisms of Lignin and Biomass Pyrolysis by Distributed Activation Energy Model with Genetic Algorithm

Elucidating Kinetic Mechanisms of Lignin and Biomass Pyrolysis by Distributed Activation Energy Model with Genetic Algorithm

Applicability of genetic algorithm in biochar combustion kinetics with double distributed activation energy model

Applicability of genetic algorithm in biochar combustion kinetics with double distributed activation energy model

Pseudo Master Curve Analysis of an Infinite Number of Parallel First-Order Reactions: Improved Distributed Activation Energy Model.

The so-called Distributed Activation Energy Model (DAEM) has been used extensively, mainly to analyze pyrolysis reactions of solid reactants. The model expresses many parallel first-order reactions using the distributions of activation energy f(E) and frequency factor k 0(E). Miura and Maki presented a method to estimate both f(E) and k 0(E) in the DAEM in 1998. This model has been used successfully by many researchers. In this paper more general basic equations are derived for describing an infinite number of parallel first-order reactions by extending the basic equations for the finite number of parallel first-order reactions. Revisiting the Miura-Maki method based on the general basic equations, a graphical analysis method that may be called "Pseudo Master Curve Analysis" is presented. The method not only supplements the Miura-Maki method but gives the underlying concept of the Miura-Maki method clearly. It is also shown that the graphical method can be applicable to analyze single reactions and the experimental data obtained using isothermal reaction techniques. Next, a method that improves the estimation accuracy of k 0(E) is presented. Practical examples analyzing several experimental data are also given to show the usefulness and validity of the Miura-Maki method and the graphical method. Through the examination, it is proposed that the DAEM should be renamed, for example, as the Distributed Rate Constant Model (DRCM).

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.

Experimental and kinetic study of PET pyrolysis under fast and slow heating rates using a visualized Macro TGA

A visualized macro thermogravimetric analyzer was utilized to gather data on sample weight, temperature, and image signals of centimeter-scale PET. The PET was subjected to both fast (above 300 K/min) and slow (below 25 K/min) heating rates. The experimental findings revealed that weight loss mainly occurred at different temperature ranges under fast (above 610 °C) and slow (400–520 °C) heating rates. The isoconversional method (ICM) and the distributed activation energy model (DAEM), both assuming single-step reactions, were employed separately to predict the conversion and rate of PET pyrolysis. However, the prediction error was considerable. To address this issue, a discrete distributed activation energy model (DDAEM) was developed, incorporating both single-step and double-step parallel reactions. The DDAEM yielded a prediction error within 10 %, which is better than ICM and DDAEM. Furthermore, all three models (ICM, DAEM, and DDAEM) indicated significant discrepancies in activation energies between fast and slow heating rates.

Investigation of the co-pyrolysis characteristics and gas emission properties of spent bleaching earth and biomass in a thermogravimetric analyser and a fixed bed reactor

The co-pyrolysis of spent bleaching earth (SBE) for adsorption decolorization and biomass can promote the resource utilization of industrial waste. The thermal behaviour and kinetics during the co-pyrolysis of SBE with sawdust (SD) were comparatively evaluated with thermogravimetric analysis at different mixing ratios and heat rates. Activation energies corresponding to the different conversion rates were determined by the distributed activation energy model (DAEM). The pyrolysis yield and evolved gases were measured by a fixed bed pyrolysis system. The results demonstrated that as SBE increased, the activation energy during the initial stage of pyrolysis clearly decreased. The fixed bed isothermal pyrolysis experiment showed that the increase in SBE had a significant effect on the gas production components, resulting in a decrease in CO and CO2 yields and an increase in alkane content. At 800°C, the addition of 30 % SBE had the highest H2 yield, indicating that SBE is a valuable additive.

Unlocking biosolid pyrolysis: Towards tailored biochar with different surface properties

To develop a thorough understanding of the thermal decomposition process of biosolids and the qualities of biosolid-derived biochar, this study performs a thermogravimetric analysis (TGA) of biosolids and examines the properties of biosolid-derived biochar produced from varying temperatures of pyrolysis. The pyrolysis of biosolid is conducted under varying heating rates (10, 15, 20 and 25 °C/min) until reaching the maximum temperature of 900 °C. The kinetic triplet (kinetic model, activation energy, and frequency factor) at the corresponding conversion point is determined by analysing the TGA results of the biosolids. The thermal degradation of hydrated compounds shows activation energies ranging from 80 to 100 kJ/mol, whereas the thermal decomposition of organic matter in biosolids exhibits activation energies ranging from 120 to 497 kJ/mol. As the temperature increases, the thermal reactions transition from simple surface reactions with frequency factors below 109 s−1 to more complex reactions with frequency factors above 109 s−1. The distributed activation energy model (DAEM) is established using the approximated temperature function and the activation energy distribution functions. The DAEM shows the mean activation energies of 93–128 kJ/mol, 279–287 kJ/mol and 359–377 kJ/mol for activation energy distribution peaks. The standard deviations of the mean activation energies are 30–64 kJ/mol, 23–30 kJ/mol and 23–41 kJ/mol, respectively. As the pyrolysis temperature is raised from 700 °C to 900 °C, both the specific surface area and micropore volume of biosolid-derived biochar increase, from 48.25 m2/g to 65.74 m2/g and 0.0313 cm3/g to 0.0369 cm3/g, respectively. The findings of this study demonstrate biosolid pyrolysis kinetics, which is essential for establishing a pyrolysis facility for biosolid management and producing biosolid-derived biochar with varying qualities.

Demineralization effects on physicochemical and combustion characteristics of biomass: Insights into distributed kinetics, flue gas evolution, and slag formation

Biomass as the only carbon-bearing renewable energy has enormous potential to challenge the established energy structure dominated by fossil resources, and incineration technology is one of the most direct and efficient pathways for utilizing biomass resources, unfortunately enduring the inevitable sintering and slagging problems owing to the excessive alkali metals. Herein, we comparatively investigated the effects of five leaching solvents (water, acetic acid, wood vinegar, hydrochloric acid, and oxalic acid) on the physicochemical properties and ash-removal capabilities of wheat straw (WS) and rice husk (RH), with a view to achieving better performance in the subsequent combustion characteristics, kinetic examination, flue gas, and slag evolution. Results indicated with ionization ability increased (water < acetic acid < hydrochloric acid), the WS exhibited a strong demineralization performance (maximum 61.1%), further leading to a steep weight loss in its combustion characteristic curve at approximately 350 °C and a delayed peak temperature after the removal of alkali metal. Multiple distributed activation energy model and sensitivity analysis revealed that leaching pretreatment enhanced the activation energy (189–191.8 kJ mol−1) and optimized energy distribution at the preliminary stage of the combustion reaction. In addition, the absence of alkali metals suppressed the catalytic oxidation reaction in the flue gas, remarkably limiting the formation of CO2 but facilitating the release of CO and CH4. Meanwhile, a considerable optimal in biomass ash slagging, in which the initial temperature of the liquid phase slag for WS ash increased to 991 °C. Notably, HCl showed the strongest demineralization performance among the five leaching solvents during pretreatment, but the high-temperature slag content was still higher than that of acetic acid. Therefore, slagging performance is not only associated with the demineralization ability of leaching solvents, but also with ash composition.

KINETICS AND THERMODYNAMIC ASSESSMENT OF RICE HUSK IN AN INERT ATMOSPHERE AS A FEEDSTOCK FOR ALTERNATIVE FUEL PRODUCTION

The utilisation of rice husk as a feedstock for alternative fuel production is an area of growing interest due to its abundance and potential as a renewable energy source. This study reports investigation of kinetics and thermodynamics of rice husk pyrolysis in an inert atmosphere. Experimental analysis, including proximate, ultimate, structural composition and thermogravimetric analyses (TGA), were conducted to determine the proxanal, ultanal, chemical composition and pyrolysis characteristics of rice husk under inert conditions. Kinetics of the pyrolysis process was evaluated using distributed activation energy model (DAEM) while thermodynamic parameters such as activation energy (E A), changes in enthalpy (ΔH), entropy (ΔS),and Gibbs free energy (ΔG) were computed to provide insights into the reaction mechanisms. The feedstock exhibited ash content, fixed carbon, volatile matter, and higher heating value on dry basis of 13.56wt%, 16.37wt%, 70.07wt% and 15.22MJ/kg respectively while the result of ultimate analysis showed carbon, hydrogen, nitrogen, sulphur and oxygen content of 40.95, 5.67, 0.22, 0.09 and 52.17wt%. The chemical composition result (water extractives-free) indicated cellulose, hemicellulos and lignin content of 39.12, 17.56 and 22.43 wt%. The kinetics analysis revealed that the pyrolysis process followed a single-order reaction mechanism and irreversible, suggesting that the pyrolysis reactions proceed in a direction that favors the formation of products. The average E A, ΔH, ΔS and ΔG required for the pyrolysis reactions was established to be 140.56 kJ/mol, 137.00 kJ/mol, -135.25 J/mol and 222.38 kJ/mol respectively. The comprehensive assessment of the feedstock affirms its suitability for alternative fuel production towards a greener energy landscape.

Comprehensive investigation of almond shells pyrolysis using advance predictive models

This research focused on comprehensive characterization and assessment of almond shells pyrolysis for bioenergy potential through thermogravimetric analysis from ambient temperature to 900 °C at different heating rates of 10, 15, and 20 °C/min in inert environment. Iso-conversional model-free methods like Friedman, Ozawa-Flynn-Wall (OFW), and Kissinger-Akahira-Sunose (KAS) were used for kinetic analysis. Average activation energies (Ea) evaluated using Friedman, OFW, and KAS methods were 198.45 kJ mol−1, 204.43 kJ mol−1, and 204.97 kJ mol−1, respectively. The evaluation of thermodynamic parameters, including ΔH‡, ΔG‡, and ΔS‡, was also assessed. The average values of ΔH‡, ΔG‡, and ΔS‡, were found to be 199.4 kJ mol−1, 172.17 kJ mol−1 and 42.60 kJ mol−1 respectively. The reaction mechanism was obtained from combined kinetics. A high R2 value of 0.9933 demonstrates strong agreement between the combined kinetic analysis results and the experimental data. The distribution activation energy model was assessed employing four pseudo elements identified as PC1, PC2, PC3, and PC4. Artificial Neural Network (ANN) and Boosting regression trees (BRT) were used for the prediction of Ea of almond shells pyrolysis. The detailed understanding of thermokinetics and creating customized predictive and innovative modelling techniques like ANN and BRT sets a new benchmark for developing customized models for thermochemical conversion of varieties of almond shells.

Comprehensive kinetic modeling and product distribution for pyrolysis of pulp and paper mill sludge

Pyrolysis holds immense potential for clean treatment of pulp and paper mill sludge (PPMS), enabling efficient energy and chemical recovery. However, current understanding of PPMS pyrolysis kinetics and product characteristics remains incomplete. This study conducted detailed modeling of pyrolysis kinetics for two typical PPMSs from a wastepaper pulp and paper mill, namely, deinking sludge (PPMS-DS) and sewage sludge (PPMS-SS), and analyzed comprehensively pyrolysis products. The results show that apparent activation energy of PPMS-DS (169.25–226.82 kJ/mol) and PPMS-SS (189.29–411.21 kJ/mol) pyrolysis undergoes significant change, with numerous parallel reactions present. A distributed activation energy model with dual logistic distributions proves to be suitable for modeling thermal decomposition kinetics of both PPMS-DS and PPMS-SS, with coefficient of determination >0.999 and relative root mean square error <1.99 %. High temperature promotes decomposition of solid organic materials in PPMS, and maximum tar yield for both PPMS-DS (53.90 wt%, daf) and PPMS-SS (56.48 wt%, daf) is achieved at around 500 °C. Higher levels of styrene (24.45 % for PPMS-DS and 14.71 % for PPMS-SS) and ethylbenzene (8.61 % for PPMS-DS and 8.33 % for PPMS-SS) are detected in tar and could be used as chemicals. This work shows great potential to propel development of PPMS pyrolysis technology, enabling green and sustainable production in pulp and paper industry.

Hydrochars derived via wet torrefaction of empty fruit bunches: Effect of temperature and time, comparison to oil palm trunks counterpart, and their pyrolysis behavior

In this study, hydrochars derived from the wet torrefaction of empty fruit bunches (EFB) were characterized and compared to those of oil palm trunks (OPT). Then, the kinetics modelling of EFB-derived hydrochars was evaluated and compared with the Distributed Activation Energy Model (DAEM) under logistics distribution via thermogravimetric analysis (TGA) under pyrolytic conditions at different heating rates. Bench-scale pyrolysis of EFB-derived hydrochars were also performed and characterized. This study elucidates the effect of prolonged residence time (3–72 hours) at different temperatures (180–220 °C) on the wet torrefaction of EFB, and comparison to OPT provides an understanding of wet torrefaction mechanisms. The pyrolysis kinetics of EFB-derived hydrochars provide insights into their pyrolysis behavior and their potential in pyrolytic application. Increased temperature and residence time enhanced the higher heating value (HHV) of the hydrochars at the expense of low mass yield. Hydrochars obtained at 220 °C and 72 hours had the highest HHV at 27.4 ± 0.5 MJ kg−1 with a mass yield of 38.3 ± 2 wt%. EFB-derived hydrochars had a higher mass yield than OPT-derived hydrochars. The van Krevelen diagram revealed that dehydration was the primary reaction pathway for EFB and OPT-derived hydrochars. SEM showed the formation of secondary deposits on both EFB and OPT hydrochars. EFB-derived hydrochars obtained at 220 °C and 72 hours had the highest mean activation energy (E0) with a distribution of activation energy (σ) from 176.7 to 181.7 kJ mol−1 and 43.4–49.9 kJ mol−1, respectively. The increased mean and distribution of activation energies were attributed to the lignin-dense structure of the hydrochars. The kinetic parameters of the hydrochars were also independent of heating rates at low heating rates (< 20 °C min−1). The thermal stability of the pyrochars obtained from EFB-derived hydrochars enabled their applications in fields such as carbon support, activated carbon, water purification process, or carbon sequestration.

Heat and mass transfer analysis of coal coking process in the coking chamber

ABSTRACT To study the coking heat mass transfer process and reveal the law of industrial-scale coal pyrolysis, the heat transfer characteristics of coal material in the coking process are analyzed based on coke oven temperature measurement experiments. A mathematical model of the coking process in the coking chamber was constructed based on the distributed activation energy model. The heat transfer process of the coal feed, generation of coke oven gas, and dynamic precipitation characteristics of each component during the coking cycle were further studied. The results show that tar and water are the earliest released and fastest precipitated pyrolysis products, respectively, which are completely precipitated at 800 K. The contents of the components of the inward and outward gases are obviously different, with CH4 and H2 accounting for 73.79% of the outward gas, while H2O and tar account for 77.80% of the inward gas. When the coal reaches 1200 K, all pyrolysis products except H2 are precipitated completely. The model can effectively predict the changes of raw coke oven gas composition during the coking process at different locations in the coking chamber.

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.

Pyrolysis mechanism and pyrolysis kinetics of yellow wine lees.

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

Thermal oxidation characteristics of polystyrene with different particle sizes based on the traditional kinetic approaches and distributed activation energy model

Thermal oxidation characteristics of polystyrene with different particle sizes based on the traditional kinetic approaches and distributed activation energy model

Valorization of waste PET: Understanding the role of active ammonia in facilitating PET depolymerization and aromatic nitrile formation

Realizing the recovery and valorization of waste polyethylene terephthalate (PET) plastics into value-added products have gained significant importance. This study successfully synthesized aromatic nitriles, specifically terephthalonitrile (TPN), from waste polyethylene terephthalate (PET) plastic through in situ catalytic pyrolysis with urea and γ-Al2O3 catalyst. Based on distributed activation energy model, positive interaction between waste PET and urea is responsible for improved thermal decomposition kinetics. The dosage of urea and pyrolysis temperature significantly influenced TPN production. TPN yield reached 32.5% with ca. selectivity of 85% at 550 °C and equivalent urea dosage. Density functional theory calculations validated the role of active ammonia in reducing energy barriers and thus facilitating PET depolymerization. The study highlights the feasibility of recycling waste PET into valuable aromatic nitriles through in situ catalytic pyrolysis with urea and enhances the understanding of the pyrolysis process.

New criteria to select reasonable hyperparameters for kinetic parameter estimation in distributed activation energy model (DAEM) by using neural network

The utilization of biomass is being actively explored to reduce net emissions of CO2. Solid carbon such as biomass is a mixture of various components that are difficult to separate, and it is not easy to evaluate its reactivity. The distributed activation energy model (DAEM) is often used to evaluate the reactivity of solid feedstocks such as biomass and coal. In our previous study, we proposed DAEM-NN, a method to estimate the model parameters using a neural network. In this study, we propose a new criterion Φ for selecting the optimal hyperparameters in DAEM-NN: by minimizing Φ, we can select hyperparameters that maximize both the conversion prediction accuracy and the typical importance of each reaction in a parallel reaction system. To verify the usefulness of the proposed criterion, reaction data were generated by numerical simulation, and the number of hidden layer, and the lower limit of contribution were optimized to minimize Φ. The hyperparameters that minimize Φ reduced the set of kinetic parameters corresponding to less important responses from the DAEM-NN kinetic analysis results.

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

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