Dimethyl ether (DME) and dimethoxymethane (DMM) as reaction enhancers for methane: Combining flame experiments with model-assisted exploration of a polygeneration process

Abstract

The potential of dimethyl ether (DME) and dimethoxymethane (DMM), representatives of the attractive oxymethylene ether (OME) alternative fuel family, are explored here as reactivity enhancers for methane-fueled polygeneration processes. Typically, such processes that can flexibly generate power, heat, or chemicals, operate under fuel-rich conditions in gas turbines or internal combustion engines. To provide a consistent basis for the underlying reaction mechanisms, it is recognized that speciation data for the DME/CH4 fuel combination are available for such conditions while such information for the DMM/CH4 system is largely lacking. In addition, it should be noted that a detailed speciation study in flames, i.e., combustion systems involving chemistry and transport processes over a large temperature range, is still missing in spite of the potential of such systems to provide extended species information. In a systematic approach using speciation with electron ionization molecular-beam mass spectrometry (EI-MBMS), we thus report, as a first step, investigation of six fuel-rich premixed flames of DME and DMM and their blends with methane with special attention on interesting chemicals. Secondly, a comprehensive but compact DME/DMM/CH4 model (PolyMech2.1) is developed based on these data. This model is then examined against available experimental data under conditions from various facilities, focusing preferentially on elevated pressure and fuel-rich conditions. Comparison with existing literature models is also included in this evaluation. Thirdly, an analysis is given on this basis, via the extensively tested PolyMech2.1 model, for assumed polygeneration conditions in a homogeneous charge compression ignition (HCCI) engine environment. The main interest of this model-assisted exploration is to evaluate whether addition of DME or DMM in a polygeneration process can lead to potentially useful conditions for the production of syngas or other chemicals, along with work and heat. The flame results show that high syngas yields, i.e., up to ∼78% for CO and ∼35% for H2, can be obtained in their burnt gases. From the large number of intermediates detected, predominantly acetylene, ethylene, ethane, and formaldehyde show yields of 2.1−4.4% (C2 hydrocarbons) and 3.4−8.7% (CH2O), respectively. Also, methanol and methyl formate show comparably high yields of up to 0.6−6.7% in the flames with DMM, which is 1–2 orders of magnitude higher than in those with DME as the additive. In the modeling-assisted exploration of the engine process, the PolyMech2.1 model is seen to perform at significantly reduced computational costs compared to a recently validated model without sacrificing the prediction performance. Promising conditions for the assumed polygeneration process using fuel combinations in the DME/DMM/CH4 system are identified with attractive syngas yields of up to 77% together with work and heat output at exergetic efficiencies of up to 89% with DME.