Formate species in the low-temperature oxidation of dimethyl ether

The oxidation of dimethyl ether (DME, 340 ppm in 10% O2) has been studied experimentally in an atmospheric pressure laminar flow reactor in the temperature range from 240 degrees C to 700 degrees C for residence times in the range 2-4 s. The influence of nitric oxide additions up to 620 ppm to the feed gases has also been investigated. Products of reaction were determined by FTIR. In the absence of NO, reaction is first detected at about 260 degrees C. The products in the low-temperature region include formaldehyde (HCHO), and formic acid (HCOOH). The addition of NO leads to the appearance of methyl formate (CH3OCHO). While the overall behaviour of the system can be explained qualitatively in terms of typical low-temperature hydrocarbon ignition, recently published chemical kinetic models for DME ignition do not allow for the formation of these formate species. We find no experimental evidence for the formation of hydroperoxymethyl formate (HPMF, HOOCH2OCHO) which is predicted by the models to be a significant stable intermediate at temperatures below 350 degrees C. Since both formic acid and methyl formate have potentially harmful health effects, these observations may have significant implications for use of DME as a diesel fuel.