Improved method for kinetic parameters estimation of non-isothermal reaction: Application to residuum thermolysis

Yang, Junwei; Wang, Lanjuan; Tian, Cuifang; Xiao, Jiazhi; Yang, Chaohe

doi:10.1016/j.fuproc.2012.07.007

Cited by 5 publications

(8 citation statements)

References 14 publications

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“…The cracking rate of bonds between different species decreases in the following order: saturates > aromatics > resins > asphaltenes The presence of long-chain saturates in the form of cross-linkages between heavier species induces faster global cracking kinetics when compared with oils with lesser saturate contents . Recently, Yang and his co-workers proposed an eight-parallel-lump kinetic model for the upgrading of undisclosed type vacuum residue. They estimated a global rate constant of 0.30 h –1 for the thermal cracking of the heavy oil, which is in close agreement with the global rate constant estimated for ALVR in this study.…”

Section: Resultsmentioning

confidence: 99%

“…They estimated a global rate constant of 0.30 h –1 for the thermal cracking of the heavy oil, which is in close agreement with the global rate constant estimated for ALVR in this study. Other global rate constants estimated by different authors , for the thermal cracking of different residua are also found in reasonable agreement with the estimated value in this study. Figure shows the global rate constants estimated by a number of authors in addition to that estimated in the current study for the thermal cracking of different residua.…”

Section: Resultsmentioning

confidence: 99%

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Kinetic Modeling of Arab Light Vacuum Residue Upgrading by Aquaprocessing at High Space Velocities

Fathi

Pereira‐Almao

2013

Ind. Eng. Chem. Res.

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Aquaprocessing (AQP) is a novel method that offers higher conversion level under asphaltenes stability limit. It is a process of steam catalytic cracking using unsupported ultradispersed catalyst. Following a 2011 published work by Fathi and Pereira on upgrading a paraffinic residuum from Arab Light Vacuum Residue (ALVR) by AQP, this work investigates a proposed lumped kinetic model for the upgrading of ALVR via AQP for the first time. The model is evaluated based on experimental results conducted in a continuous upflow open tubular pilot-plant reactor under short-space times and under conditions distant from coke formation. The proposed model is based on five cascaded lumps generated at and below the asphaltenes stability limit: 540 °C+ ALVR, VGO (455−540 °C), distillates (204−455 °C), naphtha (IBP−204 °C), and gases. The model compositions are found close to the experimental values with mean absolute percentage errors (MAPEs) of <5.5%.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Kinetic Modeling of Arab Light Vacuum Residue Upgrading by Aquaprocessing at High Space Velocities

Fathi

Pereira‐Almao

2013

Ind. Eng. Chem. Res.

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“…This can be done by calculating an equivalent temperature for each run. This equivalent temperature is the temperature that under isothermal conditions would give the same product yields for the same reaction time as the nonisothermal temperature profile in question . The method used for calculating the equivalent temperature value is given below.…”

Section: Methodsmentioning

confidence: 99%

Levulinic Acid Production from Starch Using Microwave and Oil Bath Heating: A Kinetic Modeling Approach

Mukherjee

Dumont

2016

Ind. Eng. Chem. Res.

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This work examines the role played by starch composition and heating media in the synthesis of the promising biorefinery chemical levulinic acid (LA). Three corn starches with different amylose/amylopectin ratios were converted to LA using both microwave and conventional oil bath heating. The results obtained for the different reaction temperatures and times were used to calculate kinetic parameters using a multireaction model. It was observed that the long preheating and cooling times employed in microwave heating led to equivalent reaction temperatures below the set temperatures, and this in turn affected the product distributions via changes in the reaction kinetics. At low reaction temperatures, high amylopectin waxy corn starch gave higher LA yields than normal or high-amylose corn starch. Similarly, LA yields were higher at lower temperatures for oil bath heating than for microwave heating. The maximum LA yield obtained was around 53−55% for all substrates and for both heating media, but was obtained for a shorter reaction time and at a lower equivalent temperature in the case of microwave heating.

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“…The existence and importance of reactions occurring on cooling has been recognized in the literature. The issue has been discussed in connection with decomposition of amino acids [6], pyrolysis of hydrocarbons [7], cracking of heavy oils [8], pyrolysis of heterogeneous materials such as almond shells, municipal solid waste, lignin, and polyethylene [9]. It has also been brought up in regard to epoxy materials crosslinking [10,11] and vulcanization of rubber [12,13,14,15].…”

Section: Pragmatic Motivationmentioning

confidence: 99%

All You Need to Know about the Kinetics of Thermally Stimulated Reactions Occurring on Cooling

Liavitskaya

Vyazovkin

2019

Molecules

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In this tutorial overview article the authors share their original experience in studying the kinetics of thermally stimulated reactions under the conditions of continuous cooling. It is stressed that the kinetics measured on heating is similar to that measured on cooling only for single-step reactions. For multi-step reactions the respective kinetics can differ dramatically. The application of an isoconversional method to thermogravimetry (TGA) or differential scanning calorimetry (DSC) data allows one to recognize multi-step kinetics in the form of the activation energy that varies with conversion. Authors’ argument is supported by theoretical considerations as well as by experimental examples that include the reactions of thermal decomposition and crosslinking polymerization (curing). The observed differences in the kinetics measured on heating and cooling ultimately manifest themselves in the Arrhenius plots of the opposite curvatures, which means that the heating kinetics cannot be used to predict the kinetics on cooling. The article provides important background knowledge necessary for conducting successful kinetic studies on cooling. It includes a practical advice on optimizing the parameters of cooling experiments as well as on proper usage of kinetic methods for analysis of obtained data.

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Improved method for kinetic parameters estimation of non-isothermal reaction: Application to residuum thermolysis

Cited by 5 publications

References 14 publications

Kinetic Modeling of Arab Light Vacuum Residue Upgrading by Aquaprocessing at High Space Velocities

Kinetic Modeling of Arab Light Vacuum Residue Upgrading by Aquaprocessing at High Space Velocities

Levulinic Acid Production from Starch Using Microwave and Oil Bath Heating: A Kinetic Modeling Approach

All You Need to Know about the Kinetics of Thermally Stimulated Reactions Occurring on Cooling

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