Energy-saving investigation of vacuum reactive distillation for the production of ethyl acetate

Ethyl acetate (EtAc) reactive distillation (RD) configurations often use atmospheric pressure, and this operating pressure can be reduced further to conserve energy based on the condenser cooling water temperature. Using the Aspen Plus simulator, two proposed configurations, RD column with stripper and pressure swing reactive distillation (PSRD), were simulated at lower operating pressure. The impact of RD column operating pressure on total energy usage and total annual cost (TAC) was studied. All design parameters were optimized using sequential iterative optimization procedures and sensitivity analysis to minimize the energy cost while maintaining the required product purity at 99.99%. The simulation results showed that the RD column with a stripper is better than PSRD with a saving of 23.17% in TAC and 31.53% in the specific cost of EtAc per kg. Compared to literature results, the proposed configurations have lower reboiler duty requirements and lower cost per kg of EtAc.

Calcium Glycerolate Catalyst Derived from Eggshell Waste for Cyclopentadecanolide Synthesis

The synthesis costs of macrolide musks are higher than those of other commercial musks. To make this process less expensive, eggshell waste was calcined at a low temperature to obtain a catalyst for the cyclopentadecanolide production via reactive distillation using a glycerol entrainer. X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy analyses of the original and recovered catalysts revealed that the main catalytic ingredient was calcium glycerolate (CaG) and not calcium diglyceroxide (CaDG). The basic strengths of CaG and CaDG obtained by Hammett indicators were 7.2 < H_≤ 15.0 and 9.8 < H_≤15.0, while the corresponding base amounts were 1.9 and 7.3 mmol/ g, respectively. Because CaG was soluble in glycerine, the catalyst was efficiently reused. The reaction product containing over 95.0% cyclopentadecanolide with a yield of 49.8% was obtained at a temperature of 190°C and catalyst amount of 12 wt% after 7 h of reaction. Thus, eggshell waste may be directly placed into the reaction mixture after calcination at 600°C to synthesise a large amount of cyclopentadecanolide within a relatively short time. The results of this work indicate that eggshell waste can serve as a potential eco-friendly and affordable catalyst source for the production of macrolide musks.

Intensification of an Irreversible Process using Reactive Distillation– Feasibility Studies by Residue Curve Mapping

Reactive distillation processes are very promising in substituting Sconventional liquid phase reaction processes. However this technology is not suitable for all kind of processes or types of reaction. Therefore, assessing the feasibility of these process concepts forms an important area in current and future research and development activities. The present paper focuses on the feasibility studies based on the construction of residue curve maps for the toluene methylation system. The RCMs were constructed and analyzed; it is concluded that the process of synthesis of xylenes when carried out in the reactive distillation column enhances the selectivity of the desired para isomer. Keywords: Reactive Distillation, Residue Curve Maps, Feasibility Study, Toluene Methylation, Aspen Plus

Synthesis of Brominated Alkanes via Heterogeneous Catalytic Distillation over Al2O3/SO42−/ZrO2

Concentrated sulfuric acid is generally used as a catalyst for producing brominated alkanes in traditional methods, but is highly corrosive and difficult to separate. This work reports the preparation of bromopropane from n-propanol based on a reactive distillation strategy combined with alumina-modified sulfated zirconia (Al2O3/SO42−/ZrO2) as a heterogenous catalyst. As expected, under the optimum reaction conditions (110 °C), the yield of bromopropane was 96.18% without side reactions due to the reactive distillation strategy. Meanwhile, the microscopic morphology and performance of Al2O3/SO42−/ZrO2 were evaluated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunner–Emmet–Teller (BET), Fourier transform infrared spectroscopy (FT–IR), and other characterization methods. The results confirmed that the morphology of zirconia sulfate is effectively regulated by the modification method of alumina, and more edges and angles provide more catalytic acid sites for the reaction. Furthermore, Al2O3/SO42−/ZrO2 exhibited high stability and remarkable reusability due to the strong chemical bond Zr–Al–Zr. This work provides a practical method for the preparation of bromopropane and can be further extended to the preparation of other bromoalkanes.