Sulfonic Acid Functionalization of Different Zeolites and Their Use as Catalysts in the Microwave-Assisted Etherification of Glycerol with tert-Butyl Alcohol

Molecules. 2017 Dec 12;22(12):2206. doi: 10.3390/molecules22122206.

Abstract

The etherification of glycerol with tert-butyl alcohol in the liquid phase, over different sulfonic acid functionalized zeolites, has been studied. The reaction was carried out using microwaves as a way of heating, measured at autogenous pressure and without any solvent. Dealuminated HY and HZSM-5 zeolites by acid treatment were functionalized with two different organosilica precursors: 3-mercaptopropyltrimethoxysilane (M), which incorporates thiol groups, and 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane (C), which incorporates the sulfonic acid groups directly. The thiol groups were oxidized into sulfonic groups employing hydrogen peroxide. The textural and structural properties of the solids were studied by XRD and N₂ adsorption-desorption isotherms, whereas the incorporation of the organosilica in the zeolites was studied by TGA and XPS. The novelty functionalization of M gave rise to solids with the highest acidity, and exhibited the highest yields with more substituted ethers (Yh-GTBE = 13%), at 75 °C and 15 min of reaction time. In addition to the acidity, the textural properties of the zeolites played an important role in their activity; HY, with the largest size of the channels, were more active than the HZSM-5.

Keywords: etherification; glycerol; microwave; organosilica precursor; tert-butyl alcohol; zeolite functionalization.

MeSH terms

  • Catalysis
  • Ethers / chemical synthesis*
  • Gas Chromatography-Mass Spectrometry / methods
  • Glycerol / chemistry*
  • Hydrogen Peroxide / chemistry
  • Microwaves
  • Nitrogen / chemistry
  • Sulfonic Acids / chemistry*
  • Zeolites / chemistry*
  • tert-Butyl Alcohol / chemistry*

Substances

  • Ethers
  • Sulfonic Acids
  • Zeolites
  • Hydrogen Peroxide
  • tert-Butyl Alcohol
  • Nitrogen
  • Glycerol