Quantitative 1H NMR spectroscopy was used to study chemical equilibria and reaction kinetics of both the formation and decomposition of 1,3,5-trioxane in aqueous formaldehyde solutions. The reaction was homogeneously catalyzed with up to 0.10 g g(-1) sulfuric acid at temperatures between 360 and 383 K so that most of the experiments had to be carried out pressurized. The studied mixtures were complex due to the formation of methylene glycol and poly(oxymethylene) glycols in aqueous formaldehyde and the presence of considerable amounts of ionized species. Most common internal standards are decomposed by the hot sulfuric acid and external standards were not applicable using the flow NMR probe or pressurizable NMR sample tubes. Therefore, for the quantification of the small trioxane signals, a novel procedure was applied, in which electronically generated NMR signals were used as highly stable Virtual References (VR). The NMR decoupler channel with wave-form generator was used as the source of the reference signal, which was irradiated into the probe using the lock coil. Details on the experimental procedure are presented. It is shown that the presented method yields reliable quantitative reaction data for the complex studied mixtures.
Acetaldehyde is an important intermediate in the chemical industry and often used in mixtures with water. These mixtures are reactive multicomponent systems, as acetaldehyde forms oligomers with water. Quantitative studies of the resulting speciation are scarce in the literature and limited to the formation of the smallest oligomer, ethane-1,1-diol. Therefore, in the present work, a comprehensive study of chemical equilibria in mixtures of acetaldehyde and water was carried out by quantitative 1 H-and 13 C-NMR spectroscopy. The study covers temperatures between 275 and 338 K and overall acetaldehyde mole fractions between about 0.05 and 0.95 mol/mol. The peak assignment is given for both the 1 H-and 13 C-NMR spectra. From the speciation data, obtained from the peak area fractions, numbers for the chemical equilibrium constants of the oligomer formation are obtained and a correlation is presented.
Mixtures
of acetaldehyde and water are reactive multicomponent systems because
poly(oxymethylmethylene) glycols are formed. A study on the kinetics
of the formation of these oligomers was carried out using a new microreactor
NMR probe head that combines online flow 1H NMR spectroscopy
with microreaction technology. The study covers temperatures between
278 and 298 K and pH values between 3.5 and 10.3. From the peak areas
in the 1H NMR spectra, quantitative results for the conversion
of acetaldehyde were obtained. On the basis of the new data, a reaction
kinetic model was developed and numbers for the kinetic constants
of poly(oxymethylmethylene) glycol formation were determined together
with a correlation that describes their dependence on the temperature
and pH value.
Dividing Wall Columns (DWCs) allow the separation of a ternary mixture in one column shell by applying a vertical partition wall, yielding a reduction of operational and capital costs of up to 30%. Multiple DWC (mDWC), the consequent advancement of standard DWC, makes use of more than one partitioning wall, allowing the separation of quaternary or even higher mixtures in one column shell accompanied by a further reduction of energy consumption. Since no dedicated models for these columns are available in commercial process simulators, thermodynamic consistent flowsheets have to be designed and implemented. The thermally fully coupled Petlyuk arrangement is one important example. However, the initial convergence of these substituting flowsheets is demanding, since a large number of meaningful initial guesses have to be provided. A promising method for generating these first estimates are minimum vapor (V min ) diagrams. All internal flows can be extracted from these diagrams and used for robust initialization of the simulation. The goal of this work is to present the V min method in a comprehensive way in order to initialize mDWC simulations to predict the separation of four component mixtures. Additionally, the adaptation of the diagram to configurations different than Petlyuk arrangements for mDWC is evaluated and a systematic procedure to obtain them is presented. In the end, an example of a converging simulation is given, which was obtained with the values from the V min diagram.
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