Study of pyrolysis kinetics of Alberta oil sand by thermogravimetric analysis

The kinetics of the thermal decomposition of Alberta oil sand has been investigated by thermogravimetric analysis (TGA) for the study of oil sand pyrolysis characteristics. The TGA experiments were carried out at four different heating rates of 10, 20, 30, 40 °C/min up to 900 °C to verify weight variation and reaction temperature. The activation energy of the thermal decomposition of Alberta oil sand obtained from the kinetic analysis was similar to that of the previous researches. Also, bitumen was extracted by solvent (toluene, THF (tetrahydrofuran)) and analyzed. Extracted bitumen was analyzed by using proximate analysis, ultimate analysis, heavy metal analysis, heating value, asphaltenes, API, SIMDIS, density, TLC, and molecular weight. The analyses of the extracted bitumen were similar to those of heavy residue.     

TGA studies of asphaltenes derived from cold-lake (Canada) bitumen

The pyrolysis of the asphaltene fraction from Cold-Lake, Canada, bitumen in a nitrogen environment in the temperature range 20–845°C has been studied by TGA. A rate equation for the decomposition of asphaltenes was derived and a second order decomposition of asphaltenes was observed. The apparent activation energy and the Arrhenius constant for the decomposition of the asphaltenes were calculated and found to be 56.5 kcal/mol and 5.2 × 10¹⁸g^?1 min^?1, respectively.     

五彩湾煤和吐鲁番煤热解动力学模型评估与应用

煤热解是煤热加工利用的基础反应,热解动力学模型有助于预测煤在热解过程中挥发分脱除规律,当前文献中已报道了多种热解动力学模型,厘清不同热解模型参数选择的差异,评估不同模型对煤种及热解反应适应性可为热解工艺设计提供参考。采用¹³C NMR核磁共振测量了五彩湾煤和吐鲁番煤的碳化学结构,并使用热重法测量了不同加热速率下的两种低阶煤失重曲线,结合分段式单一速率扫描法、等转化率法和3段式高斯分布活化能模型（3-DAEM）分析热重实验数据。结果表明单一速率扫描法得出的动力学参数难以准确揭示热解反应机理;等转化率法可以较好地得出热解活化能及指前因子分布图;将等转化率方法获得的指前因子赋值给分布活化能模型,可以避免分布活化能模型指前因子选择的盲目性;3-DAEM模型仅需要一条TGA曲线便可获得适用于整个加热速率的动力学参数,其预测结果与实验数据吻合最好,且模拟得出的活化能分布图很好地反映了煤热解三个阶段特征。     

饱和水介质条件下油页岩热解动力学

利用高压釜反应装置,对柳树河油页岩进行了热压模拟实验研究,考察了饱和水介质条件下油页岩的热解动力学。利用不同温度下热解产物的实验数据,建立了以沥青为中间产物的连串一级反应的动力学模型,得到了相关的动力学参数,结果表明,油母质热解生成热沥青的活化能约为110 kJ·mol^-1,低于热沥青进一步分解生成页岩油的活化能（约为190 kJ·mol^-1）,说明油母质热解生成热沥青的反应更容易进行。根据实验数据和动力学结果,对油页岩的热解机理和水介质的影响进行了初步探讨。结果表明,在饱和水介质条件下,油页岩的热解温度比无水条件时降低了约120℃。     

Thermal cracking and combustion kinetics of asphaltenes derived from Fosterton oil

Thermal behavior of crude oil (Fosterton) asphaltenes mixed with reservoir sand was investigated using thermogravimetric analysis (TGA), in nitrogen and air atmospheres for different heating rates up to 800 °C. In this study, four sets of TGA runs were performed to examine the thermal behavior of Fosterton asphaltenes and the coke derived from the asphaltenes. The parameters studied were heating rate (10, 15 and 20 °C min^− 1) and the type of purge gas (N₂ and air) employed for the process of thermal degradation of asphaltenes. Distributed activation energy model (DAEM) has been applied to study the asphaltene pyrolysis kinetics. It was observed that the activation energy was distributed from 46.16 to 72.17 kJ/mol, for the conversion range of 0.1 to 0.4. The general model for nth order reaction was used to obtain the kinetic parameters of coke oxidation reaction from the TGA data. From the model, the calculated activation energy, E, was 93.46 kJ/mol and the pre-exponential factor was 9.59 × 10⁵ min^− 1 for the coke combustion. The apparent order of combustion reaction gradually increased from 0.7 to 0.8 for different temperatures.     

Solvent-deficient synthesis of cerium oxide: Characterization and kinetics

The reaction mechanism and kinetics of CeO₂ synthesis using a solvent-deficient method are investigated by simultaneous thermogravimetric analysis (TGA)/differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The decomposition process of the cerium(III) nitrate hexahydrate and ammonium bicarbonate precursor mixture with four observed stages is monitored using TGA/DSC measurements in a nonisothermal regime with heating rates of 5, 10, 15 and 20?°C min^?1. The proposed mechanism indicates a complex synthesis with several parallel reactions, some of which occur at room temperature. A detailed kinetic analysis is performed using isoconversional (expanded Friedman, modified Coats-Redfern and Kissinger) and model fitting (N^th order and nucleation and growth models) methods. The first three stages are best described by the N^th order model with activation energy values of 21, 53 and 90?kJ?mol^?1. The last stage, during which ammonium nitrate decomposition occurs, is best fit by the nucleation and growth model and has an activation energy of 129?kJ?mol^?1. The proposed mechanism, supported by the kinetic analysis in our study, indicates that CeO₂ has already formed before the reaction reaches 200?°C. The average crystallite size of CeO₂ synthesized at 300?°C, which was calculated from the XRD measurements and observed in the SEM and TEM data, is between 10 and 20?nm.     

Evaluation of the pyrolytic and kinetic characteristics of Enteromorpha prolifera as a source of renewable bio-fuel from the Yellow Sea of China

The pyrolytic and kinetic characteristics of Enteromorpha prolifera from the Yellow Sea were evaluated at heating rates of 10, 20 and 50 °C min^?1, respectively. The results indicated that three stages appeared during pyrolysis; dehydration, primary devolatilization and residual decomposition. Differences in the heating rates resulted in considerable differences in the pyrolysis of E. prolifera. Specifically, the increase of heating rates resulted in shifting of the initial temperature, peak temperature and the maximum weight loss to a higher value. The average activation energy of E. prolifera was 228.1 kJ mol^?1, the pre-exponential factors ranged from 49.93 to 63.29 and the reaction orders ranged from 2.2 to 3.7. In addition, there were kinetic compensation effects between the pre-exponential factors and the activation energy. Finally, the minimum activation energy was obtained when a heating rate of 20 °C min^?1 was used.     

Pyrolysis of pitch derived from hydrocracked athabasca bitumen

Results of isothermal and temperature-programmed pyrolysis experiments in an inert atmosphere and at temperatures from 350 to 1000 °C are presented. Thermogravimetric techniques using a recording microbalance were employed for following the weight changes occurring during the pyrolysis. Several techniques including ¹³C n.m.r., gas chromatography, mass spectrometry and standard ASTM methods were used to analyse the decomposition products and the unreactive char. The bulk of the weight loss, as much as 35% by weight of the original sample, occurs at temperatures below 500 °C. The mechanism of pyrolysis can be adequately described as proceeding in two stages. During the first stage, when about 20% of the sample decomposes, the pyrolytic reactions follow overall firstorder kinetics. During this stage the apparent activation energy and the pre-exponential factor both increase with increasing extent of reaction and exhibit a kinetic compensation effect. During the remainder of the pyrolysis, the activation energy decreases with increasing extent of reaction and the kinetics become complex.     

The pyrolysis of bitumen-impregnated sandstone in short contact time reactors,I. Cyclone reactor

The concept of a short contact time, cyclone reactor has been evaluated for the pyrolysis of bitumen-impregnated sandstone from the Whiterocks and PR Spring tar sand deposits of the State of Utah. Approximately, 18 s were required for a 0.025 cm diameter bitumen-impregnated sand particle to achieve 90% conversion of the bitumen to hydrocarbon products. Thermal analysis data (TGA) was obtained as a function of particle size to determine the extent of bitumen conversion to products: hydrocarbon liquids and gases and a carbonaceous residue on the sand. The extent of the pyrolysis reaction or the conversion decreased with increased sand particle size at a fixed pyrolysis temperature and reaction time.A 400-cm diameter cyclone reactor would provide adequate residence time at pyrolysis temperatures to achieve greater than 90% conversion of the bitumen to hydrocarbon liquids and to C₁–C₄ hydrocarbon gases for sand particles having a diameter less than 0.03 cm. The cyclone reactor does not provide adequate retention time for sand particles having a diameter in excess of 0.1 cm, however, a riser-cyclone reactor would permit the processing of larger diameter particles.     

Study of sawdust pyrolysis and its devolatilisation kinetics

Pyrolysis of sawdust was studied using a thermogravimetric analyser (TGA) to understand the devolatilisation process and to obtain its global kinetic parameters. The influences of particle size, initial weight of the sample and heating rate on the devolatilisation of sawdust particles have been studied. Results from proximate analysis show that smaller particle size has more ash content compared to larger particle size. The TG and derivative TG curve for variation in particle size and initial weight of the sample showed significant difference in the third stage of the pyrolysis. In addition, the pyrolysis of sawdust differed significantly for variation in heating rate. As the heating rates increased, the char yield also increased. The devolatilisation kinetics was studied considering different stages of pyrolysis. The kinetic parameters for thermal devolatilisation of the sawdust were determined through a nonlinear optimisation method of two independent parallel nth‐order reaction models. The kinetic parameters such as activation energy, frequency factor and order of the reaction for the two stages considered in the model were: E₂ = 79.53 (kJ/mol), E₃ = 60.71 (kJ/mol); k₀₂ = 1.90 × 10⁶ (1/min), k₀₃ = 1.01 × 10³ (1/min); n₂ = 0.91, n₃ = 1.78, respectively. The results show good agreement between the proposed model and the experimental data of the sawdust pyrolysis.     

Chain reaction mechanism of cellulose pyrolysis

Chatterjee and Conrad¹ studied the kinetics of pyrolysis of cotton cellulose in the temperature range 270–310°C and proposed a chain reaction mechanism. Lipska and Parker⁸ studied the pyrolysis of the α-cellulose in the temperature range 250–300°C and interpreted the kinetic data differently. Both articles were published almost simultaneously. In this paper Lipska and Parker's complete data have been again analyzed and reinterpreted in light of the chain reaction mechanism. The energies of activation for initiation and propagation steps of the cellulose decomposition reaction are discussed.     

Effect of particle size on thermal decomposition and devolatilization kinetics of melon seed shell

Thermogravimetric analysis (TGA) and devolatilization kinetics of melon seed shell (MSS) at different particle sizes (150?µm and 500?µm) and at different heating rates (10, 15, 20, and 25?°C/min) were investigated with the aid of TGA. The results of the TGA analysis show that the TGA curves corresponding to the first and third stages for 150?µm particle sizes exhibited some bumps that developed at the first and third stages of pyrolysis. It was also observed that at constant heating rate, the maximum peak temperature increases as the particle sizes increase from 150 to 500?µm, whereas 500?µm particle sizes exhibited higher peak temperatures compared to 150?µm particle sizes. The resulting TGA data were applied to the Kissinger (K), Kissinger–Akahira–Sunose (KAS) and Flynn–Wall–Ozawa (FWO) methods and kinetic parameters (activation energy, E and frequency factor, A) were determined. The E and A obtained using K method were 74.27?kJ mol^?1 and 3.84?×?10⁵?min^?1 for 150?µm particle size, whereas for 500?µm particle size were 97.12?kJ mol^?1 and 3.74?×?10⁷?min^?1, respectively. However, the average E and A obtained using KAS and FWO methods were 82.35?kJ mol^?1, 1.29?×?10⁷?min^?1, and 88.50?kJ mol^?1, 1.32?×?10⁷?min^?1 for 150?µm particle sizes. While for 500?µm particle sizes, the E and A were 108.46?kJ mol^?1, 3.14?×?10⁹?min^?1, and 113.05?kJ mol^?1, 7.56?×?10⁹?min^?1, respectively. It was observed that E and A calculated from FWO and KAS methods were very close and higher than that obtained by K method. It was observed that the minimum heat required for the cracking of MSS particles into products is reached later at higher peak temperatures since the heat transfer is less effective as they are at lower peak temperatures.     

Thermal oxidative degradation kinetics of PP and PP/mg (OH)2 flame‐retardant composites

The thermal stability and thermal oxidative degradation kinetics of polypropylene (PP) and flame‐retardant PP composites filled with untreated and treated magnesium hydroxide (MH) in air were studied by thermogravimetric analysis (TGA). The effect of the heating rate in dynamic measurements (5°C–30°C/min) on kinetic parameters such as activation energy was also investigated. The Kissinger and Flynn–Wall–Ozawa methods were used to determine the apparent activation energy for the degradation of neat PP and flame‐retardant PP composites. The results of TGA showed that the addition of untreated or treated MH improved the thermal oxidative stability of PP in air. The kinetic results showed that the apparent activation energy for degradation of flame‐retardant PP composites was much higher than that of neat PP, suggesting that the flame retardant used in this work had a great effect on the mechanisms of pyrolysis and combustion of PP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1978–1984, 2007     

美国绿河油页岩中沥青热解特征及动力学

沥青是油页岩中的重要有机质,也是油页岩中油母质热解产油和气过程的重要中间产物,对其热解研究有利于加深油页岩/油母质热解理解。通过索氏萃取提取出了绿河油页岩中的沥青,并对其进行了不同升温速率下热解实验。基于热重（TGA）数据,使用Friedman法计算了沥青热解的活化能,并通过活化能分布特征,推测沥青热解可能包含三个过程。接着,使用双高斯函数对含有交叠峰的DTG曲线进行反褶积处理,分解成三个峰,依次对应每一个过程。使用最小二乘法获得了这三个过程的活化能、指前因子和反应模型通式,并将获得的通式与四类固态物质热解模型中的11种理想模型进行对比,辨识出上述三个过程均遵循n级反应模型。     

Enthalpies of pyrolysis and oxidation of Athabasca oil sands

Thermal degradation of Athabasca oil sands, bitumen, and its fractions have been investigated in N₂and in air, at 25–600 °C and at pressures up to 6.9 MPa, using thermogravimetry (TG) and high pressure differential scanning calorimetry (PDSC). These conditions are likely to occur during in-situ recovery of bitumen by underground combustion processes. Two regions of weight loss are detected using both gases. The endothermic low temperature volatilization reactions (150–400 °C) absorbed +26 mJ mg^?1 for oil sand to +2319 mJ mg^?1 for medium oil. The heats of reaction for high-temperature cracking and volatilization reactions (400–550 °C) were similar. The heats of reaction for the low-temperature oxidation reactions (150–375 °C) were ?405 mJ mg^?1 for oil sand to ?30200mJ mg^?1 for medium oil. Values for the high-temperature oxidation reactions (400–550 °C) were slightly higher. Increasing the pressure of nitrogen and air caused an increase in the endothermicity and exothermicity of the respective reactions.     

Kinetics of wood phenolysis in the presence of HCL as catalyst

Monarch birch wood (Betula maximowiczina Regel) wastes were phenolated in the presence of HCl as a catalyst at 60–150°C for various reaction times. Typical kinetic parameters along with percent reacted wood and phenol were determined by using kinetic models. In addition, according to the transition‐state theory the activation parameters of wood phenolysis was determined. The percent reacted wood wastes depicted that about 90% of the wood could be liquefied into phenol at a temperature of 150°C. However, about 30% of phenol was found to react with wood components. The kinetic studies showed that wood phenolysis with HCl catalyst at 60–150°C obviously followed a bimolecular type of second‐order reaction. Activation energy was found to be 13.438 kJ mol^?1 from an Arrhenius plot. Furthermore, the findings related with activation enthalpy showed that the wood phenolysis had dominantly endothermic reaction nature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1098–1103, 2002     

A comparison of fluidized bed pyrolysis of oil sand from Utah,USA, and Alberta,Canada

Characterization and thermal pyrolysis of oil sand was conducted. The experiment was performed on Circle Cliffs, Utah, U.S.A. and the results were compared with the data from Alberta, Canada. The reaction character identified by TGA was dual mode of vaporization of light hydrocarbon and thermal cracking of high molecular hydrocarbon. The pyrolysis experiment was performed in a 2 kg/h capacity fluidized bed externally heated by electricity. The process variables investigated were a temperature range of 723-923 K, fluidization gas velocity of 1.5-2 times of the minimum fluidization velocity, solid retention time of 15-30 minutes, and average particle size of 435 microns. The results of TGA and elemental analysis of bitumen provided necessary information regarding maximum liquid yield from the pyrolysis prior to pyrolysis experiment. The oil yield was maximum at 823 K. The yield of liquid was not exceeding the weight percent of maltenes in original bitumen. The optimum reaction condition should be fast vaporization of light hydrocarbon and minimizing thermal cracking of high molecular hydrocarbon. To maximize the liquid yield, fast heating and vaporization of oil sand bitumen and then the rapid removal of the vaporized product from the heating zone is recommended, i.e., operation in a fluidized bed reactor.     

PERFORMANCE OF ACIDIC MCM-LIKE ALUMINOSILICATE CATALYSTS IN PYROLYSIS OF POLYPROPYLENE

Mesoporous aluminosilicate catalysts having different Al/Si ratios were synthesized following a hydrothermal synthesis route and using different aluminum sources, such as aluminum nitrate and aluminum isopropoxide. These mesoporous materials have high surface areas, in the range of 520–1001 m²/g, and exhibit Type IV nitrogen adsorption isotherms. EDS and ²⁷Al MAS NMR results showed that aluminum was incorporated more effectively into the structure of the catalyst forming a tetrahedral framework when aluminum nitrate was used as the aluminum source. The activities of these catalysts in the polypropylene pyrolysis reaction were tested in a TGA apparatus. Results showed a marked reduction in the degradation temperature in the presence of aluminosilicate catalysts. The activation energy of degradation was 172 kJ/mole without any catalyst. However, using the mesoporous aluminosilicate catalysts synthesized by using aluminum nitrate as the aluminum source, activation energy of the degradation reaction decreased to values of about 24–28 kJ/mole.     

Identification of the combustion behaviour of lignite char between 350 and 900 °C

The combustion behaviour of four different lignite samples pyrolysed at 800 and 1000 °C has been studied. The reaction order and the activation energy of the char combustion reaction can be easily determined from the time to reach 50% conversion. Under 550 °C the reaction order of lignite samples are 0.7 and the activation energies are 27.4–27.9 kcal gmole^?1. Above 550 °C the measurement of the intrinsic reaction rate is limited by the film diffusion resistance. The pyrolysis temperature affects the reactivity significantly. The reactivity of char pyrolysed at 800 °C is 3.5 times that of char pyrolysed at 1000 °C.     

Modeling process kinetics in Cu/C nanocomposite synthesis

We have studied the kinetics of chemical transformations in polyacrylonitrile (PAN) and composite Cu/PAN (C _Cu = 10% (mass)) at P = 10^?5 Pa in the range of temperatures of 20–700°C during heating according to the linear law with a velocity of 10°C/min with the method of thermogravimetry. From the conducted kinetic studies of pyrolysis, it can be inferred that kinetic data of the destruction reaction of PAN and a composite of Cu/PAN are described with differential dependences on the basis of heterogeneous chemical reaction equations. Experimental data prove the heterogeneous reactions of the first order. The limiting stages of the process depend on the kinetic processes of chemical bonds opening in the polymer and composite. For the reaction of composite Cu/PAN in a vacuum, the determinant is the decomposition of copper salt and a PAN complex with the formation of copper nanoparticles at 470–570 K.