On the anhydrous synthesis of oxymethylene dimethyl ether by the reaction of dimethoxymethane with gaseous molecular formaldehyde
Abstract: The aim of this thesis was the development of novel synthetic routes and -processes for the synthesis of the sustainable synthetic fuel oxymethylene dimethyl ether (OME; CH3(-OCH2-)nO-CH3, n = 3-5). A novel homogeneously catalyzed OME-synthesis was established by the reaction of dimethoxymethane (OME1) with anhydrous gaseous formaldehyde (FA). By the use of catalytic amounts of the synthesized compound OMe3+[Al(OC(CF3)3)4]−, the reaction could be performed at very mild reaction conditions (25-30 °C, ambient pressure) without the use of additional solvent. However, catalyst-separation and -recyclability for homogenously catalyzed reactions is difficult. Because of this, the above-mentioned synthesis was enhanced by the immobilization of the homogenous catalyst in a second reaction-phase. Using the ionic Liquid (IL) 1-Ethyl-3-methylimidazolium tetrafluoroborate (EMIM+BF4–), two phases were formed. The lower phase consisted of the IL with the commercially available dissolved OMe3+BF4−-catalyst. The upper phase consisted of the starting material OME1. By vigorously stirring the two-phasic mixture, an emulsion was formed to which gaseous FA was initiated. After the FA-initiation has been completed, the stirring was stopped and the two phases reformed. The lower phase contained the immobilized catalyst and the upper phase consisted of the OME-product-mixture. With the use of this biphasic approach, the IL-catalyst-solution could be reused at least ten times and highly pure OME-mixtures were formed.
The above-mentioned syntheses were performed in liquid OME1 in the condensed phase. To obtain a continuous process, the biphasic reaction concept was further improved towards a Supported Ionic Liquid Phase (SILP)-process. For this purpose, the homogeneous OMe3+BF4–-catalyst was dissolved in the IL EMIM+BF4– and the resulting solution was immobilized on a porous support material. The resulting SILP-particles, which contained the catalytically active IL-catalyst-solution on their surface, were filled in fixed-bed reactors and the gaseous substrates (OME1 and FA) were continuously passed over the catalyst bed. In order to perform this reaction, an almost completely automated catalytic test stand was configured and assembled, and different SILP-catalyst were synthesized. Analyzed via gas-chromatography, the successful continuous, gaseous formation of OME was confirmed.
Thereby, the novel OME-synthesis based on OME1 and gaseous FA was transferred from a purely homogenous synthesis to a biphasic process. Moreover, these batch-phase processes were enhanced to a continuous, gas-phase synthesis of OME
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Notes
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Universität Freiburg, Dissertation, 2021
- Keyword
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Methyl ether
Formaldehyde
- Event
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Veröffentlichung
- (where)
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Freiburg
- (who)
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Universität
- (when)
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2021
- Creator
- DOI
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10.6094/UNIFR/220821
- URN
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urn:nbn:de:bsz:25-freidok-2208218
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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25.03.2025, 1:45 PM CET
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
Time of origin
- 2021
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