Innovative BPPO Anion Exchange Membranes Formulation Using Diffusion Dialysis-Enhanced Acid Regeneration System

Recycling of acid from aqueous waste streams is crucial not only from the environmental point of view but also for maturing the feasible method (diffusion dialysis). Anion exchange membrane (AEM)–based diffusion dialysis process is one of the beneficial ways to recover acid from aqueous waste streams. In this article, the synthesis of a series of brominated poly (2, 6–dimethyl-1, 4–phenylene oxide) (BPPO)-based anion exchange membranes (AEMs) through quaternization with triphenylphosphine (TPP) were reported for acid recovery via diffusion dialysis process. The successful synthesis of the prepared membranes was confirmed by Fourier transform infrared (FTIR) spectroscopy. The as-synthesized anion exchange membranes represented water uptake (WR) of 44 to 66%, ion exchange capacity of (IEC) of 1.22 to 1.86 mmol/g, and linear swelling ratio (LSR) of 8 to 20%. They exhibited excellent thermal, mechanical, and acid stability. They showed homogeneous morphology. The acid recovery performance of the synthesized AEMs was investigated in a two compartment stack using simulated mixture of HCl and FeCl2 as feed solution at room temperature. For the synthesized anion exchange membranes TPP–43 to TPP–100, the diffusion dialysis coefficient of acid (UH+) was in the range of 6.7 to 26.3 (10−3 m/h) whereas separation factor (S) was in the range of 27 to 49 at 25 °C. Obtained results revealed that diffusion dialysis performance of the synthesized AEMs was higher than the commercial membrane DF–120B (UH+ = 0.004 m/h, S = 24.3) at room temperature. It showed that the prepared AEMs here could be excellent candidates for the diffusion dialysis process.

A chromatography-free and aqueous waste-free process for thioamide preparation with Lawesson’s reagent

After completing the thio-substitution with Lawesson’s reagent, ethanol was found to be effective in the decomposition of the inherent stoichiometric six-membered-ring byproduct from the Lawesson’s reagent to a highly polarized diethyl thiophosphonate. The treatment significantly simplified the following chromatography purification of the desired thioamide in a small scale preparation. As scaling up the preparation of two pincer-type thioamides, we have successfully developed a convenient process with ethylene glycol to replace ethanol during the workup, including a traditional phase separation, extraction, and recrystallization. The newly developed chromatography-free procedure did not generate P-containing aqueous waste, and only organic effluents were discharged. It is believed that the optimized procedure offers the great opportunity of applying the Lawesson’s reagent for various thio-substitution reactions on a large scale.

A Column-Free and Aqueous Waste-Free Process for Thioamide Preparation with Lawesson’s reagent

After completing thio-substitution with the Lawesson’s reagent, ethanol was found to be able to efficiently decompose the inherent stoichiometric six-membered-ring by-product from the Lawesson’s reagent to a highly polarized diethyl thiophosphate. This treatment could significantly simplify the following column purification of the desired thioamide in a small scale preparation. As scaling up the preparation of two pincer-type thioamides, we have successfully developed a convenient process with ethylene glycol to replace ethanol during the workup, including traditional phase-cut, extraction, and re-crystallization. The newly developed column-free procedure did not generate P-contained aqueous waste, and only organic effluents were discharged. It was believed that the optimized procedure can greatly provide opportunity of the application of the Lawesson’s reagent for various thio-substituted reacions in scaling up preparation.