DFT-based microkinetic modeling of ethanol dehydration in H-ZSM-5

Alexopoulos, Konstantinos; John, Mathew; Borght, Kristof Van der; Galvita, Vladimir; Reyniers, Marie Françoise; Marin, Guy

doi:10.1016/j.jcat.2016.04.020

Cited by 78 publications

(127 citation statements)

References 53 publications

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“…Moreover, the authors considered ethanol absorption more important than water in determining the selectivity and the change of mechanism during the conversion. For a more specific comparison, we report the results obtained for the most probable routes to ethylene [A/1-2-3-4-5] and DEE [B/1-6-7-8-9] as extracted from the above-cited paper [75] (Table 18). [74].…”

Section: Ch Ch Oh + Ch Ch O ⟶ Ch Ch Och Ch + Oh (R28)mentioning

confidence: 99%

“…Reproduced from [74] where the superscript Al denotes a surface unsaturated Al site. An extended representation of the process was outlined by Alexopoulos et al [75] for the already mentioned zeolite HZSM5: the parallel ethylene/DEE figure is modified into a three-fold macro-scheme (Figure 13), where the paths A, B, and C represent in turn a succession of simultaneous and competing elementary steps.…”

Section: Ch Ch Oh + Ch Ch O ⟶ Ch Ch Och Ch + Oh (R28)mentioning

confidence: 99%

“…Table 18. Data from reference [75]: any step being reversible, equilibrium constants are always calculated via the Eyring model, while E a and A refer to the Arrhenius formulation, and are defined only for rate determining steps (RDS). These, in turn, are selected by the authors on the basis of a statistical screening of the K eq values over a larger range of temperatures and catalyst coverage.…”

Section: Ch Ch Oh + Ch Ch O ⟶ Ch Ch Och Ch + Ohmentioning

confidence: 99%

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Process Simulation for the Design and Scale Up of Heterogeneous Catalytic Process: Kinetic Modelling Issues

et al. 2017

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Abstract:Process simulation represents an important tool for plant design and optimization, either applied to well established or to newly developed processes. Suitable thermodynamic packages should be selected in order to properly describe the behavior of reactors and unit operations and to precisely define phase equilibria. Moreover, a detailed and representative kinetic scheme should be available to predict correctly the dependence of the process on its main variables. This review points out some models and methods for kinetic analysis specifically applied to the simulation of catalytic processes, as a basis for process design and optimization. Attention is paid also to microkinetic modelling and to the methods based on first principles, to elucidate mechanisms and independently calculate thermodynamic and kinetic parameters. Different case studies support the discussion. At first, we have selected two basic examples from the industrial chemistry practice, e.g., ammonia and methanol synthesis, which may be described through a relatively simple reaction pathway and the relative available kinetic scheme. Then, a more complex reaction network is deeply discussed to define the conversion of bioethanol into syngas/hydrogen or into building blocks, such as ethylene. In this case, lumped kinetic schemes completely fail the description of process behavior. Thus, in this case, more detailed-e.g., microkinetic-schemes should be available to implement into the simulator. However, the correct definition of all the kinetic data when complex microkinetic mechanisms are used, often leads to unreliable, highly correlated parameters. In such cases, greater effort to independently estimate some relevant kinetic/thermodynamic data through Density Functional Theory (DFT)/ab initio methods may be helpful to improve process description.

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Section: Ch Ch Oh + Ch Ch O ⟶ Ch Ch Och Ch + Oh (R28)mentioning

confidence: 99%

Section: Ch Ch Oh + Ch Ch O ⟶ Ch Ch Och Ch + Oh (R28)mentioning

confidence: 99%

Section: Ch Ch Oh + Ch Ch O ⟶ Ch Ch Och Ch + Ohmentioning

confidence: 99%

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Process Simulation for the Design and Scale Up of Heterogeneous Catalytic Process: Kinetic Modelling Issues

et al. 2017

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“…An extended representation of the process was outlined by Alexopoulos et al [67] for the already mentioned zeolite HZSM5: the parallel ethylene / DEE figure is modified into a three-fold macroscheme (Figure 13), where the paths A, B and C represent in turn a succession of simultaneous and competing elementary steps. These authors consider again only the catalyst oxygen atoms as directly involved in the bond activation process, however their extended reaction network was able to reproduce a set of contextually collected data without further adjusting the parameters.…”

Section: ) + ⇌mentioning

confidence: 99%

Section: ) + ⇌mentioning

confidence: 99%

Kinetic Modelling at the Basis of Process Simulation for Heterogeneous Catalytic Process Design

Tripodi¹,

Compagnoni²,

Martinazzo³

et al. 2017

Preprint

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Process simulation represents an important tool for plant design and optimisation, either applied to well established or to newly developed processes. Suitable thermodynamic packages should be selected in order to properly describe the behaviour of reactors and unit operations and to precisely define phase equilibria. Moreover, a detailed and representative kinetic scheme should be available to predict correctly the dependence of the process on its main variables. This review points out some models and methods for kinetic analysis specifically applied to the simulation of catalytic processes, as a basis for process design and optimisation. Attention is paid also to microkinetic modelling and to the methods based on first principles, to elucidate mechanisms and calculate thermodynamic and kinetic parameters. Different case histories support the discussion. At first, we have selected two basic examples from the industrial chemistry practice, e.g. ammonia and methanol synthesis, which may be described through a relatively simple reaction pathway. Then, a more complex reaction network is deeply discussed to define the conversion of bioethanol into syngas/hydrogen or into building blocks, such as ethylene.

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Integrated Full‐Spectrum Solar Energy Catalysis for Zero‐Emission Ethylene Production from Bioethanol

Deng

Batmunkh

et al. 2021

Adv Funct Materials

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Ethylene, a hydrocarbon (C2H4), is one of the widely used products in the chemical industry. A traditional dehydration method of ethanol to ethylene relies strongly on high‐temperature and high‐pressure process with significant energy consumption. In this regard, producing ethylene from bioethanol through dehydration is a promising and sustainable approach, but, this process under mild conditions results in low yields and poor selectivity. Herein, an integrated solar energy catalytic system driven by only sun energy under ambient conditions is established for the first time for bioethanol dehydration using oxygen‐vacancy‐abundant (Ov) WO3 coupled with a thin layer of carbon coating (CL) (WO3−x@C). A record‐high ethylene selectivity of 98.1% is achieved driven by full solar spectrum without any external power, featuring zero pollution emission nature. In this process, Ov acts as a solid acid center, which is the key to initiate the dehydration of ethanol to ethylene via a solar thermal process, while the CL promotes solar thermal synergy, ensuring the high reaction temperature and hot carriers transmission simultaneously. In‐situ infrared spectroscopy and thermodynamic calculations demonstrate a novel proton hydrogen‐mediated catalytic process over WO3−x@C. This work provides a new opportunity of using full‐spectrum solar energy for catalytic generation of value‐added chemicals.

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DFT-based microkinetic modeling of ethanol dehydration in H-ZSM-5

Cited by 78 publications

References 53 publications

Process Simulation for the Design and Scale Up of Heterogeneous Catalytic Process: Kinetic Modelling Issues

Process Simulation for the Design and Scale Up of Heterogeneous Catalytic Process: Kinetic Modelling Issues

Kinetic Modelling at the Basis of Process Simulation for Heterogeneous Catalytic Process Design

Integrated Full‐Spectrum Solar Energy Catalysis for Zero‐Emission Ethylene Production from Bioethanol

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