Ab Initio Multiscale Process Modeling of Ethane, Propane and Butane Dehydrogenation Reactions: A Review

Abstract

Olefins are among the most important structural building blocks for a plethora of chemical reaction products, including petrochemicals, biomaterials and pharmaceuticals. An ever-increasing economic demand has urged scientists, engineers and industry to develop novel technical methods for the dehydrogenation of parent alkane molecules. In particular, the catalysis over precious metal or metal oxide catalysts has been put forward as an alternative way route to thermal-, steam- and fluid catalytic cracking (FCC). Multiscale system modeling as a tool to theoretically understand processes has in the past decade period evolved from a rudimentary measurement-complementing approach to a useful engineering environment. Not only can it predict various experimentally obtained parameters, such as conversion, activity, and selectivity, but it can help us to simulate trends, when changing applicative operating conditions, such as surface gas temperature or pressure, or even support us in the search for the type of materials, their geometrical properties and phases for a better functional performance. An overview of the current set state of the art for saturated organic short chain hydrocarbons (ethane, propane and butane) is presented. Studies that combine at least two different dimensional scales, ranging from atomistic-, bridging across mechanistic mesoscale kinetics, towards reactor- or macroscale, are focused on. Insights considering reactivity are compared.

Kinetic Monte Carlo simulations for heterogeneous catalysis: Fundamentals, current status, and challenges

“…The DH of propane and butane on Cr 2 O 3 (0001) has also been investigated by 1p-KMC simulations. [253][254][255] Chromiun oxide catalysts are used in the so-called CATOFIN process for the production of olefins, such as propylene (from propane) and iso-butylene (from iso-butane). 255 Such studies have delivered insights into the most abundant products of the reaction pathways investigated, unwanted pathways leading to side-products or poisons, and the nature of catalyst deactivation by coking.…”

“…[253][254][255] Chromiun oxide catalysts are used in the so-called CATOFIN process for the production of olefins, such as propylene (from propane) and iso-butylene (from iso-butane). 255 Such studies have delivered insights into the most abundant products of the reaction pathways investigated, unwanted pathways leading to side-products or poisons, and the nature of catalyst deactivation by coking. In the case of DH of propane on Cr 2 O 3 (0001), 254 it was found that the accumulation of propylene and propyne in the reaction mixture adversely affects the reaction rate and selectivity.…”

Molecular Dynamics and Machine Learning in Catalysts

“…Ethylene is a necessary chemical raw material, and ethane dehydrogenation is one of the essential methods to produce ethylene. Though there is comprehensive application in industry, there are still numerous challenges [76], such as deactivation of the catalyst. The study of the ethane dehydrogenation mechanism and the funding of more effective catalysts will be helpful to confront these challenges.…”

“…Ethylene is a necessary chemical raw material, and ethane dehydrogenation the essential methods to produce ethylene. Though there is comprehensive applic industry, there are still numerous challenges [76], such as deactivation of the catal study of the ethane dehydrogenation mechanism and the funding of more effect lysts will be helpful to confront these challenges. Using density functional theory initio microkinetic model, Jalid et al [77] systematically investigated the reaction nism of ethane dehydrogenation with transition metals (Pt, Pd, Co, Ni, Rh, Ru, Au, and Ag) as catalysts and CO2 as mild oxidant.…”

Dehydrogenation of Cycloalkanes over N-Doped Carbon-Supported Catalysts: The Effects of Active Component and Molecular Structure of the Substrate

“…Furthermore, cycloalkanes are commonly used industrial chemicals which have realized long-distance transportation and large-scale storage in the chemical industry. However, the release of hydrogen in cycloalkanes is difficult because of the high thermodynamic limitation in C-H bond cleavage [5,[12][13][14]. Extensive studies found that cycloalkane dehydrogenation with heterogeneous catalysts should be carried out in gas-phase at high temperature (above 300 • C) to obtain a high hydrogen production rate and cycloalkane conversion [11].…”