Butadiene

Grub, Joachim; Löser, E.

doi:10.1002/14356007.a04_431

Cited by 11 publications

(12 citation statements)

References 42 publications

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“…Despite achievements in technologies for direct dehydrogenation of n -butene or n -butane/ n -butene mixtures (e.g., Houdry–Catadiene process), n -butene is generally used as the feedstock to achieve a high yield of 1,3-BD. Compared with significant improvements in product selectivity achieved for ethane and propane dehydrogenation, catalysts for direct n -butane dehydrogenation to 1,3-BD with high selectivity have proven more difficult to identify, , and in studies reported to date, the 1,3-BD selectivity is generally less than 20%. ,, …”

Section: Introductionmentioning

confidence: 99%

Mechanism and Kinetics of n-Butane Dehydrogenation to 1,3-Butadiene Catalyzed by Isolated Pt Sites Grafted onto ≡SiOZn–OH Nests in Dealuminated Zeolite Beta

Zhang

Leonhardt

et al. 2022

ACS Catal.

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An interest in the on-purpose production of 1,3-butadiene (1,3-BD) has grown, as a consequence of the decline in naphtha cracking for the production of ethene and propene, products that can now be produced economically by thermal dehydrogenation of ethane and propane contained in natural gas. In this study, the mechanism and kinetics of n-butane dehydrogenation to 1,3-BD are explored over atomically distributed Pt sites grafted onto dealuminated zeolite BEA (DeAlBEA) in the form of (Si–O–Zn)4–6Pt complexes. Reaction of n-butane dehydrogenation carried out at 823 K with 2.53 kPa n-butane/He and a weight-hourly space velocity (WHSV) of 14.5 h–1 produced 1,3-BD with a turnover frequency of 0.45 mol 1,3-BD (mol Pt)−1 s–1. Space-time studies and identification of the reaction intermediates suggest that n-butane first undergoes dehydrogenation primarily to 1-butene, which then rapidly isomerizes to produce an equilibrated mixture of 1-butene and 2-butene. 1-Butene then undergoes secondary dehydrogenation to produce 1,3-BD. We report, here, a detailed study of the kinetics of n-butane dehydrogenation to butenes and 1-butene dehydrogenation to 1,3-BD over isolated Pt sites. Both reactions exhibit a Langmuir–Hinshelwood dependence on n-butane and 1-butene partial pressures, respectively. Comparison of effective forward rate constants of n-butane dehydrogenation to butenes (k 1f) and butene dehydrogenation to 1,3-BD (k 2f) shows that the isolated Pt sites grafted onto DeAlBEA exhibit a very high activity for sequential dehydrogenation of n-butane to 1,3-BD relative to other Pt-based catalysts previously reported.

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Section: Introductionmentioning

confidence: 99%

Mechanism and Kinetics of n-Butane Dehydrogenation to 1,3-Butadiene Catalyzed by Isolated Pt Sites Grafted onto ≡SiOZn–OH Nests in Dealuminated Zeolite Beta

Zhang

Leonhardt

et al. 2022

ACS Catal.

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“…1,3-Butadiene (BD) is a commodity chemical with a worldwide production volume of over 14 Mt per year that finds applications as a monomer in the production of synthetic rubbers, , in the synthesis of the nylon intermediate adiponitrile, and in Diels–Alder reactions forming cycloalkanes and cycloalkenes . Traditionally, BD is obtained as a byproduct of ethylene production from steam cracking.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Study on the Lewis Acid Catalyzed Synthesis of 1,3-Butadiene over Ta-BEA Using Modulated Operando DRIFTS-MS

et al. 2016

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In recent years, the on-purpose production of 1,3-butadiene (BD) from renewable resources such as ethanol has received increased attention. In that context, Lewis acid catalysts play an important role, especially in the two-step process, i.e. when a mixture of acetaldehyde and ethanol is used as substrate. As the reaction mechanism consists of many intermediates and occurs over different catalytic functionalities, it is notoriously difficult to gain molecular-level insights into the mechanism. Here, we present a study on Lewis acidic Ta-BEA and propose a plausible reaction mechanism. We developed an operando DRIFTS-MS setup that allows for precise control and analysis of changes in the gas-phase composition as well as surface species. Using this tool, we found a surface intermediate with a vibrational frequency at 1690 cm–1 that is only formed in the presence of both ethanol and crotonaldehyde and that is likely involved in the production of BD. Our data further suggests that a subtle control of the ratio of ethanol to acetaldehyde is crucial to keep a high ethoxy coverage and to desorb the intermediate crotyl alcohol in order to achieve high BD productivity. To the best of our knowledge, this is the first dynamic operando spectroscopic study on this re-emerging reaction.

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“…The desire for more sustainable manufacturing technologies, preferably from renewable resources, has initiated significant research in the utilization of biomass‐derived feedstock using heterogeneous catalysis . The coupling of ethanol (EtOH) to 1,3‐butadiene (BD), which is an important polymer precursor with a yearly production volume of >10 Mt, is a historically important example that is currently attracting renewed attention . Traditionally, BD is obtained as a byproduct in ethylene production by steam cracking.…”

Section: Introductionmentioning

confidence: 99%

Influence of Metal Doping on the Lewis Acid Catalyzed Production of Butadiene from Ethanol Studied by using Modulated Operando Diffuse Reflectance Infrared Fourier Transform Spectroscopy and Mass Spectrometry

et al. 2017

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As a result of the increasing gap between the supply and demand of butadiene, the catalytic coupling of ethanol has regained the attention of the scientific and industrial community as an “on‐purpose” production route to butadiene. The most promising systems are based on bifunctional catalysts that comprise metal sites that can dehydrogenate ethanol to acetaldehyde and Lewis acid sites that catalyze the aldol condensation between two aldehyde molecules and the Meerwein–Ponndorf–Verley reduction of the intermediate crotonaldehyde. Here, we investigate the role of Ag in an established Ag‐Zr‐BEA catalyst using modulated operando diffuse reflectance infrared Fourier transform spectroscopy and mass spectrometry experiments. We obtain insights into the complex reaction network that involves several consecutive and parallel reactions. Based on our investigations, we formulate suggestions for catalyst optimization.

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Butadiene

Cited by 11 publications

References 42 publications

Mechanism and Kinetics of n-Butane Dehydrogenation to 1,3-Butadiene Catalyzed by Isolated Pt Sites Grafted onto ≡SiOZn–OH Nests in Dealuminated Zeolite Beta

Mechanism and Kinetics of n-Butane Dehydrogenation to 1,3-Butadiene Catalyzed by Isolated Pt Sites Grafted onto ≡SiOZn–OH Nests in Dealuminated Zeolite Beta

Mechanistic Study on the Lewis Acid Catalyzed Synthesis of 1,3-Butadiene over Ta-BEA Using Modulated Operando DRIFTS-MS

Influence of Metal Doping on the Lewis Acid Catalyzed Production of Butadiene from Ethanol Studied by using Modulated Operando Diffuse Reflectance Infrared Fourier Transform Spectroscopy and Mass Spectrometry

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