Hydration of cyclohexene to cyclohexanol in a hybrid reactive distillation with a side decanter

Nowadays, more than 1 Mt of cyclohexanol is produced each year by the direct hydration of cyclohexene according to the patented Asahi process proposed in 1990. The Asahi process involves a reactor and a separation system to recover the reactants back to the reactor and collect the pure product. The non-reacted water is recovered in a decanter and the non-reacted cyclohexene in a distillation column. Nowadays, many processes have been successfully intensified, combining several unit operations into a single unit providing savings in units, piping and often also in energy due to the synergies generated. Examples of these synergies are: the continuous removal of products push forward the reaction to total conversion overcoming the chemical equilibrium limitations; the catalyst placed in the rectifying section of the column becomes protected from heavy compounds that could poison or deactivate the catalyst; the enthalpy of reaction is directly used in the separation; the boiling point of the mixture avoids hot spots that could damage the catalyst, etc. Although its advantages, it is not widely used in the industry and further study on intensification providing further successful examples are required. The present study shows by rigorous simulation with Aspen Plus V9.0 that the Asahi process is a good candidate to be intensified in a single unit. The rigorous simulation results show that cyclohexanol is collected with a molar fraction purity of 0.9999 at the bottoms of a hybrid reactive distillation column with 11 equilibrium stages operated at total reflux, i.e. total conversion of reactants. The water is fed at the top to stage 1 and the cyclohexene on stage 3, both in equimolar flow rate. The catalyst is only placed in these three stages at the column top. A side stream from stage 6 is fed to a side decanter, where the aqueous phase is recycled to the column top (stage 1) and the organic phase to the next bottom stage, i.e. stage 7. As in the Asahi process, a great excess of water is present to push the reaction equilibrium forward. Hence, the molar ratio of water recycled vs feed to the system is of 125. The reboiler duty is 197 kJ/mol of cyclohexene, and the condenser duty is 564 kJ/mol cyclohexene due to the exothermic reaction. Therefore, a novel intensified process scheme for cyclohexene hydration is proposed

Tracing chemical evolution over the extent of the Milky Way's Disk with APOGEE Red Clump Stars

We employ the first two years of data from the near-infrared, high-resolution SDSS-III/APOGEE spectroscopic survey to investigate the distribution of metallicity and alpha-element abundances of stars over a large part of the Milky Way disk. Using a sample of ~10,000 kinematically-unbiased red-clump stars with ~5% distance accuracy as tracers, the [alpha/Fe] vs. [Fe/H] distribution of this sample exhibits a bimodality in [alpha/Fe] at intermediate metallicities, -0.9<[Fe/H]<-0.2, but at higher metallicities ([Fe/H]=+0.2) the two sequences smoothly merge. We investigate the effects of the APOGEE selection function and volume filling fraction and find that these have little qualitative impact on the alpha-element abundance patterns. The described abundance pattern is found throughout the range 5<R<11 kpc and 0<|Z|<2 kpc across the Galaxy. The [alpha/Fe] trend of the high-alpha sequence is surprisingly constant throughout the Galaxy, with little variation from region to region (~10%). Using simple galactic chemical evolution models we derive an average star formation efficiency (SFE) in the high-alpha sequence of ~4.5E-10 1/yr, which is quite close to the nearly-constant value found in molecular-gas-dominated regions of nearby spirals. This result suggests that the early evolution of the Milky Way disk was characterized by stars that shared a similar star formation history and were formed in a well-mixed, turbulent, and molecular-dominated ISM with a gas consumption timescale (1/SFE) of ~2 Gyr. Finally, while the two alpha-element sequences in the inner Galaxy can be explained by a single chemical evolutionary track this cannot hold in the outer Galaxy, requiring instead a mix of two or more populations with distinct enrichment histories.Comment: 18 pages, 17 figures. Accepted for publication in Ap