Continuous Synthesis of Oxymethylene Ether Fuels from Dimethyl Ether in a Heterogeneously Catalyzed Liquid Phase Process

Drexler, Marius; Haltenort, Philipp; Arnold, Ulrich; Sauer, Jörg

doi:10.1002/cite.202100173

Cited by 16 publications

(26 citation statements)

References 64 publications

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“…This reaction is described in the literature sometimes as reversible ,, and sometimes as irreversible. ,,,, Getting a good description of the present experimental data was not possible based on Reaction . Therefore, we have postulated a different mechanism for the formation of MeFo in the studied system, the cleavage of OME 2 , as given by Reaction .…”

Section: Chemical Reactionsmentioning

confidence: 92%

“…To keep the presentation concise, we discuss in the following only the mechanism that we have chosen in the present work for the evaluation of our experimental data. It is based on a broad range of publications ,− ,,− and was found to be best suited for our purpose. We do not claim that it is correct in all aspects.…”

Section: Chemical Reactionsmentioning

confidence: 99%

“…Unfortunately, there are several side reactions in the studied system, the most important of which is the formation of methyl formate (MeFo, HCOOCH 3 ). Several mechanisms for the formation of MeFo have been discussed in the literature; for anhydrous systems, most authors assume that it is formed by the Tishchenko reaction ,,,,,− …”

Section: Chemical Reactionsmentioning

confidence: 99%

“…The methanol must be replaced by either MAL or DME. There are many studies on anhydrous routes for the OME production, ,,− and the only industrial production processes of OME that have been realized so far belong to this class …”

Section: Introductionmentioning

confidence: 99%

“…MAL is produced on an industrial scale from formaldehyde and methanol in an acid-catalyzed reaction. ,, In recent work, catalysts have been developed for the direct oxidation of methanol to MAL and even for the hydrogenation of carbon dioxide directly to MAL, but these developments are presently still in an exploratory stage. , An interesting alternative to MAL as a starting material for the anhydrous OME production is DME. DME is a platform chemical that is produced directly from synthesis gas or by condensation from methanol and is, therefore, cheaper than MAL. ,,− Some publications consider the direct oxidation of DME to longer OME, but these works are also still in an exploratory stage. , …”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Methylal and Poly(oxymethylene) Dimethyl Ethers from Dimethyl Ether and Trioxane

Breitkreuz

Hevert

Schmitz

et al. 2022

Ind. Eng. Chem. Res.

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Poly(oxymethylene) dimethyl ethers (OME) are interesting synthetic fuels that could replace fossil diesel fuel. Therefore, economic routes for OME production have to be developed. One particularly interesting route is the synthesis of OME from dimethyl ether (DME) and formaldehyde. The principal feasibility of this route is established, but the physicochemical information on essential steps is still lacking. In particular, there is no data on the first step in this synthesis, which is the formation of methylal (MAL) from DME and formaldehyde. Kinetic batch experiments were carried out in a stirred batch autoclave with a commercially available acidic ion-exchange resin as a catalyst in the temperature range of 353−373 K for up to 200 h. Trioxane was used as a water-free source of formaldehyde. Due to the volatility of DME, the experiments were carried out under pressure; high-pressure magnetic resonance (NMR) spectroscopy was applied for the analysis. During the reaction, not only MAL but also OME are formed, as well as a side product, methyl formate (MeFo). Therefore, the equilibrium constant of the MAL formation had to be determined based on a reaction kinetic model of the entire reaction network. The formation of MAL was found to have a larger equilibrium constant than the subsequent oligomerization reactions leading to OME, but it is also much slower than these reactions.

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Section: Chemical Reactionsmentioning

confidence: 92%

Section: Chemical Reactionsmentioning

confidence: 99%

Section: Chemical Reactionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Synthesis of Methylal and Poly(oxymethylene) Dimethyl Ethers from Dimethyl Ether and Trioxane

Breitkreuz

Hevert

Schmitz

et al. 2022

Ind. Eng. Chem. Res.

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From a Batch to a Continuous Supported Ionic Liquid Phase (SILP) Process: Anhydrous Synthesis of Oxymethylene Dimethyl Ethers

Billion,

Vogel,

Schulte

et al. 2023

ChemCatChem

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Oxymethylene dimethyl ethers (OMEn; CH3(‐OCH2)n‐OCH3) are promising sustainable synthetic fuels when produced from CO2 and green H2. The synthesis pathway presented here overcomes synthetic problems and includes the reaction of dimethoxymethane (OME1) with molecular gaseous formaldehyde in a novel continuous, anhydrous reaction setup. An initially performed wide batch‐catalyst screening highlighted the salts M[NTf2]x with M = Cu+, Co2+ and Mg2+ as especially interesting catalysts (NTf2 = N(SO2CF3)2). Supported ionic liquid phase (SILP)‐catalysts were prepared on this basis and demonstrated the successful synthesis of OMEn in a continuous process. The SILP‐catalysts immobilized in the IL EMIM[BF4] showed a fast and strong deactivation, but those with the IL EMIM[NTf2] showed excellent catalytic performance and stable results in continuous operations exceeding 19 h. The influence of the weight hourly space velocity (WHSV), the reaction temperature as well as the storage conditions of the catalysts (inert vs non‐inert) were investigated. We also demonstrated that the catalysts can be stored in air for 50 days without loss of activity. The SILP‐catalysts were analyzed by NMR and IR spectroscopy. Furthermore, the thermodynamics of the reaction mechanism of some selected catalysts was calculated by DFT theory to this reaction.

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Advancements and Challenges in the Synthesis of Oxymethylene Ethers (OMEs) as Sustainable Transportation Fuels

Geitner,

Schuett,

Zechel

et al. 2024

Chemistry A European J

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The urgent need for sustainable alternatives to fossil fuels in the transportation sector is driving research into novel energy carriers that can meet the high energy density requirements of heavy‐duty vehicles without exacerbating the climate change. This concept article examines the synthesis, mechanisms, and challenges associated with oxymethylene ethers (OMEs), a promising class of synthetic fuels potentially derived from carbon dioxide and hydrogen. We highlight the importance of OMEs in the transition towards non‐fossil energy sources due to their compatibility with the existing Diesel infrastructure and their cleaner combustion profile. The synthesis mechanisms, including the Schulz‐Flory distribution and its implications for OME chain length specificity, and the role of various catalysts and starting materials are discussed in depth. Despite advancements in the field, significant challenges remain, such as overcoming the Schulz‐Flory distribution, efficiently managing water byproducts, and improving the overall energy efficiency of the OME synthesis. Addressing these challenges is crucial for OMEs to become a viable alternative fuel, contributing to the reduction of greenhouse gas emissions and the transition to a sustainable energy future in the transportation sector.

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Continuous Synthesis of Oxymethylene Ether Fuels from Dimethyl Ether in a Heterogeneously Catalyzed Liquid Phase Process

Cited by 16 publications

References 64 publications

Synthesis of Methylal and Poly(oxymethylene) Dimethyl Ethers from Dimethyl Ether and Trioxane

Synthesis of Methylal and Poly(oxymethylene) Dimethyl Ethers from Dimethyl Ether and Trioxane

From a Batch to a Continuous Supported Ionic Liquid Phase (SILP) Process: Anhydrous Synthesis of Oxymethylene Dimethyl Ethers

Advancements and Challenges in the Synthesis of Oxymethylene Ethers (OMEs) as Sustainable Transportation Fuels

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