Oxymethylene Dimethyl Ethers Research Articles

Optimization methodology combining Taguchi design and response surface method to maximize a compression ignition engine efficiency fueled with oxygenated synthetic fuel

This research examines the potential of a synthetic e-diesel and oxymethylene dimethyl ether blend in a heavy-duty single-cylinder engine. The main purpose is to find the optimal engine settings that maximize engine efficiency and minimize emissions. As the first step, a methodology was developed and applied to simplify the engine’s map into five characteristic points to be representative of the World Harmonized Transient Cycle, assigning weights to each load region. This simplification reported low error estimations for fuel consumption and NOx emissions over the cycle. After obtaining the five points, a drop-in analysis was assessed, where the fuel was evaluated with the same settings as diesel, revealing more advanced and shorter combustion with great reductions in soot emissions. Then, a group of three air management and three injection parameters was selected for optimization. A novel methodology combining Taguchi Design and Response Surface Methodology is developed and applied to find the best engine settings. By integrating these two methods, the research reduced the number of required experiments if only one method were used and maintained the goal of achieving higher thermal efficiencies with the new fuel blend compared to the diesel baseline. Significant statistical results were obtained in the Taguchi design, revealing the air management factors that most affected the responses; meanwhile, second-order models with high accuracy helped in finding the best injection parameters. Subsequently, the best settings were experimentally evaluated, and optimal conditions determined by the two methods were validated, confirming the effectiveness of the methodology. Optimization results revealed an improvement of around 2% higher efficiencies for the five tested points while achieving important average reductions of 28% less in NOx with additional decreases in CO, HC, and soot levels, all outperforming traditional diesel benchmarks. Finally, a well-to-wheel analysis using the simplified cycle confirmed a substantial reduction in carbon impact when replacing diesel with this alternative fuel. The successful application of this methodology to recalibrate an engine with an alternative fuel blend shows the potential of using these fuels in existing engines and offers a novel methodology that can be escalated and applied under the engine calibration context.

Soot and Flame Structures in Turbulent Partially Premixed Jet Flames of Pre-Evaporated Diesel Surrogates with Admixture of OMEn

In this study, the soot formation and oxidation processes in different turbulent, pre-evaporated and partially premixed diesel surrogate flames are experimentally investigated. For this purpose, a piloted jet flame surrounded by an air co-flow is used. Starting from a defined diesel surrogate mixture, different fuel blends with increasing blending ratios of poly(oxymethylene) dimethyl ether (OME) are studied. The Reynolds number, equivalence ratio, and vaporization temperature are kept constant to ensure the comparability of the different fuel mixtures. The effects of OME addition on flame structures, soot precursors, and soot are investigated, showing soot reduction when OME is added to the diesel surrogate. Using chemiluminescence images of C2 radicals (line of sight) and subsequent Abel-inversion, flame lengths and global flame structure are analyzed. The flame structure is visualized by means of planar laser-induced fluorescence (PLIF) of hydroxyl radicals (OH). The spatial distribution of soot precursors, such as polycyclic aromatic hydrocarbons (PAHs), is simultaneously measured by PLIF using the same excitation wavelength. In particular, aromatic compounds with several benzene rings (e.g., naphthalene or pyrene), which are known to be actively involved in soot formation and growth, have been visualized. Spatially distributed soot particles are detected by using laser-induced incandescence (LII), which allows us to study the onset of soot clouds and its structures qualitatively. Evident soot formation is observed in the pure diesel surrogate flame, whereas a significant soot reduction with changing PAH and soot structures can be identified with increasing OME addition.

Development of a reduced primary reference fuel – oxymethylene dimethyl ether (PRF-OMEx) mechanism for diesel engine applications

Oxymethylene dimethyl ethers (OMEx), having a chemical formula of CH3O-(CH2O)x-CH3 where x varies from 1 to 5, have been widely considered as a promising fuel to partially replace diesel in CI engines in terms of reducing soot emissions. This work is focused on developing a reduced primary reference fuel (PRF)-OMEx chemical mechanism to better describe the combustion and emission characteristics of gasoline/diesel blends with OMEx. The novelty of this work lies in the fact that the OMEx part of the mechanism is represented not only by OME3 as done in most studies found in literature, but also with other OME chain lengths that is, OME2-4 which are considered to be optimum and better represent the commercial OMEx blends. For this purpose, a detailed OMEx mechanism is reduced by applying different reduction techniques considering a wide range of operating conditions including pressure, temperatures, equivalence ratios and fuel compositions. The result is merged with an already validated PRF mechanism to form a reduced PRF-OMEx mechanism consisting of 213 species and 840 reactions. The newly formed mechanism is validated against a wide set of experimental data including ignition delay times, laminar flame speeds and species concentration profiles. Furthermore, a rigorous set of numerical simulations for various diesel-OMEx blends in a compression ignition engine are carried out at two different operating points to validate the developed mechanism. Simulation results highlight that the developed mechanism not only replicates the experimental behavior in terms of in-cylinder pressure and heat release rate but exhibits a better combustion phasing closer to experimental data when compared with other mechanisms where only OME3 is utilized to represent OMEx. Overall, the developed PRF-OMEx mechanism proves to be realistic and suitable for application in engine combustion simulations involving gasoline/diesel and OMEx blends.

Potential Analysis of Defossilized Operation of a Heavy-Duty Dual-Fuel Engine Utilizing Dimethyl Carbonate/Methyl Formate as Primary and Poly Oxymethylene Dimethyl Ether as Pilot Fuel

<div>This study demonstrates the defossilized operation of a heavy-duty port-fuel-injected dual-fuel engine and highlights its potential benefits with minimal retrofitting effort. The investigation focuses on the optical characterization of the in-cylinder processes, ranging from mixture formation, ignition, and combustion, on a fully optically accessible single-cylinder research engine. The article revisits selected operating conditions in a thermodynamic configuration combined with Fourier transform infrared spectroscopy.</div> <div>One approach is to quickly diminish fossil fuel use by retrofitting present engines with decarbonized or defossilized alternatives. As both fuels are oxygenated, a considerable change in the overall ignition limits, air–fuel equivalence ratio, burning rate, and resistance against undesired pre-ignition or knocking is expected, with dire need of characterization.</div> <div>Two simultaneous high-speed recording channels granted cycle-resolved access to the natural flame luminosity, which was recorded in red/green/blue and OH chemiluminescence.</div> <div>Selected conditions were investigated in more detail with the simultaneous application of planar laser-induced fluorescence of OH and HCHO and recording natural flame luminescence in a cycle-averaged manner.</div> <div>Poly oxymethylene dimethyl ether was used as pilot fuel, building on prior investigations. The mixture of 65 vol% Dimethyl Carbonate and 35 vol% Methyl Formate with prior verification on a passenger-car-sized engine substitutes synthetic natural gas in this study.</div> <div>Thermodynamically, the increased compression ratio up to 17.6 resulted in feasible operation and increased indicated efficiency. On the lower compression ratio of 15.48, a more comprehensive range of applicable air–fuel equivalence ratios and increased degrees of freedom regarding the pilot’s total energy share are observed compared to the base configuration with natural gas and EN590 as pilot fuel.</div> <div>The air–fuel equivalence ratio sweep from λ = 1.0–2.0 revealed predominantly premixed and high-temperature heat release via OH*. The temporal and spatial evolution shifts while leaning out the mixture with increasing gradients on the radial distribution and decouples for lean mixtures from the initial spray trajectory.</div>

A Comparative Experimental Analysis of Natural Gas Dual Fuel Combustion Ignited by Diesel and Poly OxyMethylene Dimethyl Ether

A Comparative Experimental Analysis of Natural Gas Dual Fuel Combustion Ignited by Diesel and Poly OxyMethylene Dimethyl Ether

Comparative well-to-tank life cycle assessment of methanol, dimethyl ether, and oxymethylene dimethyl ethers via the power-to-liquid pathway

Energy systems are currently transforming into configurations with a significant share of renewable energies to reduce greenhouse gas (GHG) emissions. One frequently discussed option to reduce CO2 and simultaneously provide temporary storage for fluctuating renewable energy is coupling the energy and the transport sector in a Power-to-Liquid (PtL) approach by producing synthetic fuels. The syntheses for methanol, 1-step and 2-step dimethyl ether and oxymethylene dimethyl ethers (OME3–5) are modeled using captured CO2 and hydrogen. Hydrogen is produced by electrolysis using German electricity mixes (2021, 2030) and wind power. To evaluate the environmental impacts of the different PtL pathways, a comparative well-to-tank Life Cycle Assessment (LCA) is conducted. Aspen process simulations are performed to provide material and energy balances for the LCA. The results show that the production of all PtL fuels is highly emission intensive, when using the current electricity mix and is – from an environmental point of view – not a viable option today. The GHG emissions are estimated to be between 9.3 – 16 kg CO2 equivalents/l diesel equivalent which is five to eight times that of a conventional diesel system. But already the electricity mix 2030 can drastically reduce the GHG emissions to 2.5 – 6 CO2 equivalents/l diesel equivalent. Wind will decrease these values further to 0.6 – 3.6 CO2 equivalents/l diesel equivalent. Dimethyl ether and methanol generate considerably lower impacts than OME3–5 as their production is less energy intensive. The conventional 2-step dimethyl ether synthesis and the more innovative 1-step process hardly differ.

OME[formula omitted]/air mixtures: The structure and propagation mechanism of their laminar premixed flames

Oxymethylene dimethyl ethers (CH3O(CH2O)xCH3 or OMEx) are synthetic substitutes of diesel and jet fuel. They can achieve soot-less combustion and have been shown to exhibit favourable ignition characteristics. With the aim to explore their combustion physics, the structure of their flames is analysed using the algorithmic tools of the Computational Singular Perturbation (CSP) method. It is demonstrated that the flame structure and the mechanism for its propagation is encapsulated in the fastest explosive mode, introduced by chemical dynamics in a narrow region of the flame front. This narrow region extends around the point where the maximum heat release rate (MHRR) is recorded. CSP diagnostics identify (i) reactions H + O2→ O + OH and CO + OH → CO2 + H beyond MHRR as initiating an upstream diffusion of heat and H radicals, both of which are generated by the exothermic reaction H2 + OH → H2O + H, (ii) a downstream convective motion that ensues and (iii) chemical activity that is initiated ahead of MHRR and sustained by the convective transport of fuel and oxygen. CSP also identifies differences in the action of the upstream diffusion of heat and H radicals and of the downstream transport of fuel and oxidiser. It is also shown that the fastest explosive mode far from the neighbourhood of MHRR has no influence on the structure and propagation of the flame front. Although OME2−4/air mixtures exhibit drastically different dynamics in the context of homogeneous autoignition, very small differences are recorded in terms of flame structure and propagation. The findings suggests that, since practically all major processes driving the flame front propagation are similar to those of hydrocarbons, OMEx fuels can be used as “drop-in” fuels in currently employed burners.

Investigation of the cooperative-effects of Lewis- and Brønstedt acids in homogeneously catalyzed OME fuel synthesis by inline-NMR monitoring.

Via inline-nuclear magnetic resonance measurements, the homogeneously catalyzed poly(oxymethylene dimethyl ether) fuel synthesis using trioxane and dimethoxy methane is investigated. Besides the Brønsted acid (BA) catalyst triflic acid (TfOH) different metal halides are studied as Lewis-acidic (LA) catalysts. Among the used LAs, MgCl2, the weakest based on electronegativity, reveals the highest catalytical activity. Additionally, the influence of the concentration of BA and LA is investigated. An increase in BA concentration leads to an exponential increase of the reaction rate, while increasing the concentration of the LA leads to a volcano plot with its optimum at a LA : BA ratio of 1 : 3. The influence of the LA on the electron density of the intermediate formaldehyde is concluded as the main factor for this behavior.

Soot formation analysis of OME (oxymethylene dimethyl ether) using fuel decomposition model by molecular dynamics simulation

Soot formation analysis of OME (oxymethylene dimethyl ether) using fuel decomposition model by molecular dynamics simulation

Combustion characteristics of oxymethylene dimethyl ether-diesel blends: An experimental investigation using a constant-volume combustion chamber

The combustion characteristics of oxymethylene dimethyl ether (OMEx) and its blends with diesel have been investigated using a multi-hole injector in a constant-volume combustion chamber. The results show OMEx addition can reduce the ignition delay, especially when blends of more than 50 vol% are used, at low chamber temperature. Two individual heat-release peaks are observed for OMEx during premixed combustion at 750 K, due to a pronounced low-temperature heat-release phase. The chamber temperature of 800 K can be regarded as a transition point for the behavior of burn duration as well as maximum ROHR peak, mostly caused by combustion regime transition from premixed- to diffusion combustion. It appears that there is an approximate linear relation between maximum ROHR peak and the time at which this peak occurs with injection pressure. The ignition delay of OMEx is almost insensitive to a decrease in ambient oxygen concentration. And the premixed ROHR profile, due to its high oxygen content, is very similar and only ignition delay and burn duration increase slightly. Additionally, comparisons of natural luminosity results for OMEx and diesel indicate that OMEx produces near-zero soot values. Luminosity is expected to be caused by chemiluminescence alone, which increases with injection pressure.

Continuous Anhydrous Synthesis of Oxymethylene Dimethyl Ethers by Reaction of Dimethyl Ether with Molecular Formaldehyde.

A novel gaseous synthesis route to oxymethylene dimethyl ethers (OMEn, n = 3-5) starting from CO2 and green H2 by using molecular formaldehyde (FA) and dimethyl ether (DME) is presented. The anhydrous reaction runs in a pressure free, gaseous, and continuous reaction setup. Hetero-geneous cata-lysts including zeolites and ion exchange resins (IER) are investigated, if they catalyze this reaction. While IER is almost inactive, zeolites with a 3D pore structure and an acidity exceeding ρm,H+(NH3,ads) = 250 µmol·gcat.-1 proved to be catalytically active. DME conversions of up to 2.76 mol-% are observed. The observed product gas stream compositions confirm thermo-dynamic considerations with back reactions / OMEn decomposition occurring as part of the equilibria under the investigated reaction conditions (90…180 °C). However, feed gas ratio variations (FA:DME = 1:2 to 1:9.5) highlighted the possibility to shift the product selectivity in favor of OMEn and suppress FA disproportionation to methyl formate. FA trimerization to trioxane is almost completely suppressed by running the reaction at 120 °C. The results presented here provide an important and unprecedented contribution to understand the complex reaction network in the OMEn synthesis reaction necessary to establish an energy efficient sustainable OMEn production process.

Driving mechanisms of high-cetane number, synthetic fuel autoignition: The case of OME[formula omitted

Oxymethylene dimethyl ethers (CH3O(CH2O)xCH3 or OMEx) are potential synthetic substitutes of diesel and jet fuel that can be acquired through CO2 recycling and have the unique “clean” feature that they do not contain C-C bonds in their atom chain, but only C-O, and therefore can combust without soot. Also, they present favourable ignition characteristics and high cetane numbers. In order to determine ignition control strategies, the dominant oxidation pathways must be identified. To this end, autoignition of OME2−4/air mixtures is studied using the tools of Computational Singular Perturbation algorithm. It is shown that as the length of the atom chain x increases, ignition delays become shorter. This is because, at the very early stages of the process, H-abstraction and fuel break-up reactions realize in a larger number of ways for larger x. The process develops first through a chemical runaway that tends to slow-down autoignition and then through a thermal runaway that tends to speed-up autoignition at a progressively stronger rate. It is shown that the total heat release is independent of x, although the ignition delay becomes shorter with increasing x. The two stable intermediates H2O2 and CH2O are shown to shorten ignition delays, when used as additives in the initial mixtures. It is demonstrated that OMEx synthetic fuels offer the capability of soot-less combustion, combined with ignition control.

From a Batch to a Continuous Supported Ionic Liquid Phase (SILP) Process: Anhydrous Synthesis of Oxymethylene Dimethyl Ethers

AbstractOxymethylene dimethyl ethers (OMEn; CH3(−OCH2)n−OCH3) are promising sustainable synthetic fuels when produced from CO2 and green H2. The synthesis pathway presented here overcomes synthetic problems and includes the reaction of dimethoxymethane (OME1) with molecular gaseous formaldehyde in a novel continuous, anhydrous reaction setup. An initially performed wide batch‐catalyst screening highlighted the salts M[NTf2]x with M=Cu+, Co2+ and Mg2+ as especially interesting catalysts (NTf2=N(SO2CF3)2). Supported ionic liquid phase (SILP)‐catalysts were prepared on this basis and demonstrated the successful synthesis of OMEn in a continuous process. The SILP‐catalysts immobilized in the IL EMIM[BF4] showed a fast and strong deactivation, but those with the IL EMIM[NTf2] showed excellent catalytic performance and stable results in continuous operations exceeding 19 h. The influence of the weight hourly space velocity (WHSV), the reaction temperature as well as the storage conditions of the catalysts (inert vs non‐inert) were investigated. 90 °C was identified as ideal reaction temperature. High feed‐gas flows (WHSV=15.8 h−1) are preferable in terms of product selectivity SOME2‐5>90 mol‐ % with an OME1 conversion XOME1=5.10 mol‐ % at the same time. We also demonstrated that the catalysts can be stored in air for 50 days without loss of activity. The SILP‐catalysts were analyzed by NMR and IR spectroscopy. Furthermore, the thermodynamics of the reaction mechanism of some selected catalysts was calculated by DFT theory to this reaction.

A Synergic Application of High-Oxygenated E-Fuels and New Bowl Designs for Low Soot Emissions: An Optical Analysis

Synthetic fuels significantly reduce pollutant emissions and the carbon footprint of ICE applications. Among these fuels, oxymethylene dimethyl ethers (OMEX) are an excellent candidate to entirely or partially replace conventional fuels in compression ignition (CI) engines due to their attractive properties. The very low soot particle formation tendency allows the decoupling of the soot-NOX trade-off in CI engines. In addition, innovative piston geometries have the potential to reduce soot formation inside the cylinder in the late combustion stage. This work aims to analyze the potential of combining OMEX with an innovative piston geometry to reduce soot formation inside the cylinder. In this way, several blends of OMEX-Diesel were tested using a radial-lips bowl geometry and a conventional reentrant bowl. Tests were conducted in an optically accessible engine under simulated EGR conditions, reducing the in-cylinder oxygen content. For this purpose, 2-colour pyrometry and high-speed excited state hydroxyl chemiluminescence techniques were applied to trace the in-cylinder soot formation and oxidation processes. The results confirm that increasing OMEX in Diesel improves the in-cylinder soot reduction under low oxygen conditions for both piston geometries. Moreover, using radial lips bowl geometry significantly improves the soot reduction, from 17% using neat Diesel to 70% less at the highest OMEX quantity studied in this paper.

Oxymethylene Ether (OME) Fuel Catalyst Screening Using in-situ NMR spectroscopy.

Online NMR measurements are introduced in the current study as a new analytical setup for investigation of the oxymethylene dimethyl ether (OME) synthesis. For the validation of the setup, the newly established method is compared with state-of-the-art gas chromatographic analysis. Afterwards, the influence of different parameters, such as temperature, catalyst concentration and catalyst type on the OME fuel formation based on trioxane and dimethoxymethane is investigated. As catalysts, AmberlystTM 15 (A15) and trifluoromethanesulfonic acid (TfOH) are utilized. A kinetic model is applied to describe the reaction in more detail. Based on these results, the activation energy (A15: 46.3 kJ mol -1 and TfOH: 79.8 kJ mol-1) and the order in catalyst (A15: 0.8 and TfOH: 2.2) are calculated and discussed.

A molecular investigation on the effects of OMEX addition on soot inception of diesel pyrolysis

This study aimed at revealing the atomic-level chemical pathways involved in the soot inception inhibition of diesel pyrolysis with oxymethylene dimethyl ether (OMEX) addition. Using the reactive force field parameters in molecular dynamics simulation, the results effectively identified the specific pathways of OME3 pyrolysis and soot inception, via the analysis of the conversion of three main species: CH2O, CH3O, and CH3, generated from the initial decomposition of OME3. It has been found that CH2O molecule would be converted to CO through continuous dehydrogenation, and the carbon atoms convertered into CO would not participate in forming soot precursors, thus reducing soot formation. The oxidizing groups (mainly OH) are primarily produced from the CH3O radicals. These oxidizing species would react with small gaseous soot precursors to form stable oxides, thus inhibiting soot formation. However, this influence is relatively small under conditions where no oxygen is involved. The CH3 radicals would participate in the formation of soot precursors. In this study, it was observed that the addition of OME3 did not reduce the number of main gaseous precursors of polycyclic aromatic hydrocarbons such as C2H2, C2H3, and C3H3 during diesel-OME3 co-pyrolysis, because there were reactions between CH3 radicals and C1 and C2 species to form C2 and C3 hydrocarbon products. Based on the simulation results, the process from diesel decomposition to incipient soot production under the effects of OME3 is panoramically demonstrated. It is also found that the chain length increase of OMEX with a fixed molar fraction does not influence soot inhibition noticeably. Increasing the proportion of OMEX added to diesel helps reduce soot as carbon atoms involved in the formation of soot precursors are reduced, and more oxidizing species would be produced to slow the formation of gaseous soot precursors.

Techno-Economic Analysis of Large Scale Production of Poly(oxymethylene) Dimethyl Ether Fuels from Methanol in Water-Tolerant Processes

Poly(oxymethylene) dimethyl ether (OME) are a much-discussed and promising synthetic and renewable fuel for reducing soot and, if produced as e-fuel, CO2 emissions. OME production is generally based on the platform chemical methanol as an intermediate. Thus, the OME production cost is strongly dependent on the methanol cost. This work investigates OME production from methanol. Seven routes for providing methanolic formaldehyde solutions are conceptually designed for the first time and simulated in a process simulator. They are coupled with a state-of-the-art OME synthesis to evaluate the economics of the overall production chain from methanol to OME. For a plant size of 100 kt/a, the average levelized product cost of OME is 79.08 EUR/t plus 1.31 times the cost of methanol in EUR/t.

A novel process towards the industrial realization of large-scale oxymethylene dimethyl ether production – COMET

The novel COMET process for the production of OME3-5 from MeOH and FA(aq.) solves the challenging H2O management using a reactive distillation column. The main process units are state-of-the-art and were experimentally demonstrated.

Suitable commercial catalysts for the synthesis of oxymethylene dimethyl ethers

The commercial catalysts Amberlyst 15 and 46 show high activities and selectivities for the OME synthesis with very low side product formations. However, the synthesis products of all investigated catalysts need to be neutralized before distillation.

Design of a process for the provision of methanolic formaldehyde solutions of low water content from aqueous formaldehyde solutions

Formaldehyde is an essential and widely used intermediate in the chemical industry. It is mostly handled and stored in aqueous solutions. However, some processes require methanolic formaldehyde solutions of low water content as feedstock, among them the production of the synthetic fuel poly(oxymethylene) dimethyl ether (OME). This work presents the conceptual design for a process to provide methanolic formaldehyde solutions with high yield, avoiding aqueous solution as a side product. The separation of water is achieved by a combination of thin-film evaporation and distillation. Process simulations and optimal operating points with respect to energy demand and residual water content are determined. A residual water content of 0.09 g/g in the product could not be undercut.