The remarkable effect of organic salts on 1,3,5-trioxane synthesis

Liu-Yi Yin,Hai-Yan Wang,Yu-Feng Hu

doi:10.1007/s12182-016-0124-3

Liu-Yi Yin, Hai-Yan Wang + Show 1 more

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https://doi.org/10.1007/s12182-016-0124-3

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Journal: Petroleum Science	Publication Date: Oct 14, 2016
Citations: 9	License type: CC BY 4.0

Affiliation: China University of Petroleum, Beijing

Abstract

The effects of organic salts on 1,3,5-trioxane synthesis were investigated through batch reaction and continuous production experiments. The organic salts used include sodium methanesulfonate (CH3NaO3S), sodium benzenesulfonate (C6H5NaO3S), sodium 4-methylbenzenesulfonate (C7H7NaO3S), and sodium 3-nitrobenzene sulfonate (C6H4NNaO5S). It was shown that the effects of organic salts on the yield of 1,3,5-trioxane in reaction solution and distillate follow the order CH3NaO3S < C6H5NaO3S < C7H7NaO3S < C6H4NNaO5S, which is inversely related to the charge density of the anions of the organic salts. In comparison with Cl−-based salts such as magnesium chloride, organic salts have the advantages of less formic acid generation and low corrosion. Studies on water activity revealed that the effect of organic salts on the activity of water was quite small at low concentration of organic salts. UV–visible spectroscopy and vapor–liquid equilibrium experiments were performed to uncover the mechanisms that govern such effects. The results showed that the effect of organic salts on the yield of 1,3,5-trioxane relies primarily on their ability to increase the catalytic activity of sulfuric acid and increase the relative volatilities of 1,3,5-trioxane and water and of 1,3,5-trioxane and oligomers.

Highlights

The effects of organic salts on 1,3,5-trioxane synthesis were investigated through batch reaction and continuous production experiments
It was shown that the effects of organic salts on the yield of 1,3,5-trioxane in reaction solution and distillate follow the order CH3NaO3S \ C6H5NaO3S \ C7H7NaO3S \ C6H4NNaO5S, which is inversely related to the charge density of the anions of the organic salts
The results showed that the effect of organic salts on the yield of 1,3,5-trioxane relies primarily on their ability to increase the catalytic activity of sulfuric acid and increase the relative volatilities of 1,3,5-trioxane and water and of 1,3,5-trioxane and oligomers

Summary

Introduction

1,3,5-Trioxane is attracting increasing attention as an alternative starting material to formaldehyde solution for preparing anhydrous formaldehyde which is used to manufacture disinfectant agents, acetal resins, bonding materials, pesticides, molding materials, antibacterial agents, etc. (Augeand Gil 2002). The remarkable role of halide salt additives in the Negishi reaction involving aryl zinc reagents has been reported (McCann and Organ 2014) It is ranked as one of the world’s top ten science and technology improvements in 2014 by Chemical & Engineering News. It can be concluded that the enhancement in the yield of 1,3,5-trioxane is attributed to hydration which can decrease the water activity Though these investigations covered important aspects of 1,3,5-trioxane synthesis, there is still something to be further explored, since the increase in the acid value by the addition of Cl--based salts is still very remarkable compared to that observed for sulfuric acid alone. In the present work we investigated the influence of organic salts on 1,3,5-trioxane synthesis by batch reaction and continuous production experiments.

UV–visible spectroscopy

Experimental

Results and discussion

Conclusions