Synthesis of tailored oxymethylene ether (OME) fuels via transacetalization reactions

In the field of alternative diesel fuels, so-called oxymethylene ethers (OMEs) are currently intensely investigated. Particularly OMEs of the type CH$_{3}$O(CH$_{2}$O)$_{n}$CH$_{3}$ with n = 3–5 exhibit promising fuel properties and combustion characteristics with strongly reduced particle and NO$_{x}$ emissions. According to their molecular structure, OMEs can be produced from methanol thus enabling sustainable production strategies from CO$_{2}$ and renewable resources. Compared to the methyl derivatives, analogous compounds with higher alkyl groups (oxymethylene dialkyl ethers, OMDAEs) have been investigated to a much lesser extent. Thus, commercially available OMDAEs, i.e. compounds of the type ROCH$_{2}$OR bearing ethyl, propyl, butyl and 2-ethylhexyl groups, have been studied. Furthermore, asymmetric compounds of the type R$^{1}$OCH$_{2}$OR$^{2}$ have been synthesized from the symmetric compounds employing transacetalization reactions catalyzed by zeolite BEA-25. The OMDAEs have been characterized by spectroscopic and spectrometric methods and several physico-chemical, thermodynamic and fuel-related data have been determined and compared. Despite their structural peculiarities, such as the oxygen-containing acetal moiety in the molecular backbone, all OMDAEs exhibit properties similar to conventional diesel fuels. Based on experimental and analytical data, the development of tools for the prediction of properties by a simple regression method is described. Furthermore, the suitability of group contribution modelling is investigated for OMDAE compounds

Hydrothermal, catalyst-free production of a cyclic dipeptide from lysine

The formation of cyclic dipeptides, 2,5-diketopiperazines (DKP), from lysine in aqueous solution was investigated at hydrothermal conditions (250 to 350 °C) without the addition of catalyst. The products obtained were analyzed by GC–MS combined with extensive $^{1}$H,$^{13}$C NMR analysis, after purification via preparative chromatography. The main product of the conversion of lysine, octahydrodipyrido[1,2-a:1\u27,2\u27-d]pyrazine-6,12(2H,6aH)-dione, was successfully isolated and identified. The purification/separation protocol is rapid, environmentally friendly, and highly efficient with excellent selectivity (81 wt%) in the oils obtained from the conversion of lysine at 300 °C. Performing the conversion step at higher temperatures or lysine concentrations led to the formation of complicated side products. Based on the evolution of key compounds during hydrothermal conversion of lysine, we propose a tentative mechanism for the formation of diketopiperazine. The technique presented in this work provides a novel catalyst-free pathway for the synthesis of DKP

Aldehydes and ketones in pyrolysis oil: analytical determination and their role in the aging process

Aldehydes and ketones are known to play a role in the aging process of pyrolysis oil and generally, aldehydes are known for their high reactivity. In order to discern in pyrolysis oil the total aldehyde concentration from that of the ketones, a procedure for the quantification of aldehydes by $^{1}$H-NMR was developed. Its capability is demonstrated with a hardwood pyrolysis oil at different stages of the aging process. It was treated by the Accelerated Aging Test at 80 °C for durations of up to 48 h. The aldehyde concentration was complemented by the total concentration of carbonyls, quantified by carbonyl titration. The measurements show, that the examined hardwood pyrolysis oil contained 0.31–0.40 mmol g$^{-1}$ aldehydes and 4.36–4.45 mmol g$^{-1}$ ketones. During the first 24 h, the aldehyde concentration declined by 23–39% and the ketone concentration by 9%. The rate of decline of aldehyde concentration slows down within 24 h but is still measureable. In contrast, the total carbonyl content does not change significantly after an initial decline within the first 4 h. Changes for vinylic, acetalic, phenolic and hydroxyl protons and for protons in the α-position to hydroxy, ether, acetalic and ester groups were detected, by $^{1}$H-NMR. In the context of characterizing pyrolysis oil and monitoring the aging process, $^{1}$H-NMR is a reliable tool to assess the total concentration of aldehydes. It confirms the reactivity of aldehydes and ketones and indicates their contribution to the instability of pyrolysis oil

Mesoporous H‐ZSM‐5 for the Conversion of Dimethyl Ether to Hydrocarbons

The potential of hierarchical H‐ZSM‐5 zeolites was studied for the conversion of DME to fuel‐compatible hydrocarbons. For this purpose, hierarchical H‐ZSM‐5 zeolites have been prepared from commercial H‐ZSM‐5 by desilication and organosilane‐directed hydrothermal synthesis. The zeolites were characterized by X‐ray diffraction, NH3‐TPD, DRIFTS, and N2 physisorption measurements. The catalysts have been tested in a tube reactor (1 bar, 648 K). The results indicate important structural changes in framework and acidic sites, which are significant for the synthesis of gasoline‐range hydrocarbons

Synthetic Biodegradable Polymers

XIV, 366 p.online resource