Nuclear Magnetic Resonance Analysis of Hydrothermal Reactions of Ethyl- and Octylamine in Sub- and Supercritical Water

Abstract

Hydrothermal reactions of aliphatic amines have recently gained importance in relation to the application of amines as film-forming corrosion inhibitors for steam−water cycles. The kinetics and mechanism of the hydrothermal reactions of ethylammomiun cation (EtAH + ) and n-octylammonium cation (OctAH + ) were studied for comparison with the corresponding neutral amines to elucidate their reaction products and pathways at sub-and supercritical temperatures of 300−400 °C as model reactions of aliphatic ammonium cations. We analyzed the reaction of 13 C-15 N-labeled EtAH + using NMR spectroscopy and revealed that the initial hydrolysis to ethanol, known as the main path, is followed by the elimination reaction producing ethene and the disproportionation reaction giving diethylammonium cation. The OctAH + yields octene and octanol, each of which isomerizes to thermodynamically more stable species as the major products. Comparisons were made between the reactions of the neutral amines and ammonium cations to highlight their different reactivity. The hydrolysis, alkene formation, and dehydration of alcohols to alkenes were all found to be accelerated at low pH. The formation of low-molecular-weight organic acids such as acetic acid and formic acid was not observed. These results indicate that the corrosion protection effect of film-forming amines will be maintained under practical conditions with pH values as high as around 9 to 10, and hence side reactions involving byproducts will be suppressed.