Optimal modes of side-section flow in heat-pump-assisted extractive distillation systems for separating allyl alcohol–allyl acetate mixtures with butyl propionate

Objectives. To investigate the influence of side-section flow modes on the energy efficiency of a partially thermally coupled distillation sequence (PTCDS) with a vapor recompression heat pump for the extractive distillation of an allyl alcohol–allyl acetate mixture with n-butyl propionate and identify modes under which the combined use of a PTCDS and heat pump are the most efficient.Methods. Mathematical modeling in the Aspen Plus V10 software package was used as the main research method. The local composition equation of the non-random two-liquid model was used as a model for describing the vapor–liquid equilibrium, while the Redlich–Kwong model was used to consider the non-ideal vapor phase. When modeling the conventional extractive distillation scheme and PTCDS, parametric optimization was carried out according to the criterion of the total energy costs in the column reboilers. For the economical evaluation, Aspen Process Economic Analyzer V10.1 tools were used.Results. For extractive distillation of a mixture of allyl alcohol (30 wt %) and allyl acetate (70 wt %) with n-butyl propionate as an entrainer, the minimum energy consumption was achieved at the same side-section flow mode for the variants of a PTCDS with and without a heat pump. The reduction in energy costs relative to the conventional scheme was 20% for the sequence without a heat pump and 38% for that with a heat pump. An economic assessment was made of the best options in comparison with the conventional extractive distillation scheme. The PTCDS with a heat pump had an advantage over the sequence without a heat pump only for long periods of operation.Conclusions. For the extractive distillation of an allyl alcohol–allyl acetate mixture, the optimal modes for the combined use of a PTCDS with a vapor recompression heat pump coincide with the optimal modes for a PTCDS without a heat pump.

Nickel-Catalyzed Reductive Allylation of Aldehydes with Allyl Acetates

Carbonyl allylation reactions constitute an important step in the formation of carbon–carbon reactions, and involve various related reactions that chiefly use allylmetal reagents. This report presents a nickel-catalyzed carbonyl allylation reaction using allyl acetate, which produces homoallyl alcohols in moderate to good yields, as an efficient methodology under reductive coupling conditions.

Exploring the Mechanism of Catalysis with the Unified Reaction Valley Approach (URVA)—A Review

The unified reaction valley approach (URVA) differs from mainstream mechanistic studies, as it describes a chemical reaction via the reaction path and the surrounding reaction valley on the potential energy surface from the van der Waals region to the transition state and far out into the exit channel, where the products are located. The key feature of URVA is the focus on the curving of the reaction path. Moving along the reaction path, any electronic structure change of the reacting molecules is registered by a change in their normal vibrational modes and their coupling with the path, which recovers the curvature of the reaction path. This leads to a unique curvature profile for each chemical reaction with curvature minima reflecting minimal change and curvature maxima, the location of important chemical events such as bond breaking/forming, charge polarization and transfer, rehybridization, etc. A unique decomposition of the path curvature into internal coordinate components provides comprehensive insights into the origins of the chemical changes taking place. After presenting the theoretical background of URVA, we discuss its application to four diverse catalytic processes: (i) the Rh catalyzed methanol carbonylation—the Monsanto process; (ii) the Sharpless epoxidation of allylic alcohols—transition to heterogenous catalysis; (iii) Au(I) assisted [3,3]-sigmatropic rearrangement of allyl acetate; and (iv) the Bacillus subtilis chorismate mutase catalyzed Claisen rearrangement—and show how URVA leads to a new protocol for fine-tuning of existing catalysts and the design of new efficient and eco-friendly catalysts. At the end of this article the pURVA software is introduced. The overall goal of this article is to introduce to the chemical community a new protocol for fine-tuning existing catalytic reactions while aiding in the design of modern and environmentally friendly catalysts.