The potential of di-methyl ether (DME) as an alternative fuel for compression-ignition engines: A review

This paper reviews the properties and application of di-methyl ether (DME) as a candidate fuel for compression-ignition engines. DME is produced by the conversion of various feedstock such as natural gas, coal, oil residues and bio-mass. To determine the technical feasibility of DME, the review compares its key properties with those of diesel fuel that are relevant to this application. DME’s diesel engine-compatible properties are its high cetane number and low auto-ignition temperature. In addition, its simple chemical structure and high oxygen content result in soot-free combustion in engines. Fuel injection of DME can be achieved through both conventional mechanical and current common-rail systems but requires slight modification of the standard system to prevent corrosion and overcome low lubricity. The spray characteristics of DME enable its application to compression-ignition engines despite some differences in its properties such as easier evaporation and lower density. Overall, the low particulate matter production of DME provides adequate justification for its consideration as a candidate fuel in compression-ignition engines. Recent research and development shows comparable output performance to a diesel fuel led engine but with lower particulate emissions. NO_x emissions from DME-fuelled engines can meet future regulations with high exhaust gas recirculation in combination with a lean NO_x trap. Although more development work has focused on medium or heavy-duty engines, this paper provides a comprehensive review of the technical feasibility of DME as a candidate fuel for environmentally-friendly compression-ignition engines independent of size or application.     

Poly (ether ether ketone ketone) based imidazolium as anion exchange membranes for alkaline fuel cells

An imidazolium functionalized poly (ether ether ketone ketone) (PEEKK-DImOH) anion exchange membrane (AEM) readily soluble in certain low-boiling-point solvents (isopropanol) is prepared. The solubility results are consistent with the results of molecular dynamics simulations. By varying the chloromethylation reaction temperature or concentrated sulfuric acid concentration of PEEKK, the degrees of chloromethylation of PEEKK are changed from 54% to 92%, the corresponding PEEKK-DImOH AEMs with the ion exchange capacities (IECs) of 1.14-1.65 mmol·g^-1. The PEEKK-DImOH 92% AEM shows high hydroxide conductivity (31 mS·cm^-1), suitable water uptake (94%) and acceptable swelling ratio (39%) at 60℃. In addition, the PEEKK-DImOH AEMs possess good thermal and alkaline stability. The maximum power density (46.16 mW·cm^-2) of fuel cell prepared with PEEKK-DImOH 92% AEM as exchange membrane and ionomer is much higher than that with commercial AHA membranes. All the above results indicate that the PEEKK used in this study is a promising AEM matrix material for alkaline fuel cells.     

合成气一步法制二甲醚催化剂的研究

在Cu-Zn-Al甲醇催化剂制备工艺的基础上,研制出合成气一步法制二甲醚催化剂。经过实验室试验和评价,确定了催化剂使用的最佳工艺条件：压力40 MPa,温度270～310 ℃,空速1 000～2 000 ｈ^-1,合成气中H2体积分数为70%～80%,CO体积分数6%～12%,CO₂体积分数3%～4%。在该条件下,CO转化率大于85％,二甲醚选择性大于90％,二甲醚的收率达65％以上。催化剂表现出良好的活性、选择性和稳定性。     

Semicontinuous separation of dimethyl ether (DME) produced from biomass

A ternary semicontinuous system for the separation of bio‐dimethyl ether from methanol and water is presented. The performance of eight potential control configurations, including the application of temperature inferential control, is evaluated. Dynamic simulations of the semicontinuous system and associated control scheme demonstrate that the temperature inferential control configuration is effective in achieving the separation objectives while remaining within operational limits. The semicontinuous system using the inferential temperature control scheme is simulated and shown to be economically preferable to the traditional continuous process for a range of production rates. © 2013 Canadian Society for Chemical Engineering     

Macroscopic spray characteristics and breakup performance of dimethyl ether (DME) fuel at high fuel temperatures and ambient conditions

The purpose of this work was to investigate, both experimentally and numerically, the spray behavior and atomization characteristics of dimethyl ether (DME) at high fuel temperatures and under various ambient conditions. In order to compare the theoretical and measured spray characteristics of DME fuel, macroscopic characteristics such as spray tip penetration and spray cone angle were investigated using spray visualization system with a heating system. DME atomization performance was calculated under various conditions from KIVA-3 V code and studied via analysis of the overall Sauter mean diameter (SMD) map, which is related to ambient gas temperature, ambient pressure, and fuel temperature.DME spray was found to exhibit behavior that differs from diesel spray under atmospheric condition. However, at high ambient pressure conditions, DME and diesel sprays display similar behavior. At ambient atmospheric condition, the spray cone angle of DME fuel is larger than that of diesel spray due to the occurrence of flash boiling. Variation in DME fuel temperature had little effect on spray tip penetration and spray cone angle characteristics. An increase in ambient air temperature caused an increase in DME spray cone angle due to an enhancement of the flash boiling effect. However, the DME spray cone angle showed a decreasing trend at high ambient pressure conditions when the ambient air temperature was increased. This was due to the disappearance of flash boiling and the evaporation of droplets at the exterior of the spray cone. In the overall SMD map, the increase of the ambient gas temperature and fuel temperature induced the increase of DME overall droplet size. On the other hand, the ambient gas pressure have slightly influenced on the overall SMD at a low ambient gas temperature and low fuel temperature, but the effect of the ambient gas pressure is significant at high ambient gas temperature and high fuel temperature. At high ambient gas temperature, the increase of the ambient gas pressure causes the increase of the overall SMD. At high DME fuel temperature, the decrease of the ambient gas pressure induces the increase of the overall SMD.     

An investigation of the effects of spray angle and injection strategy on dimethyl ether (DME) combustion and exhaust emission characteristics in a common-rail diesel engine

An experimental investigation was performed on the effects of spray angle and injection strategies (single and multiple) on the combustion characteristics, concentrations of exhaust emissions, and the particle size distribution in a direct-injection (DI) compression ignition engine fueled with dimethyl ether (DME) fuel. In this study, two types of narrow spray angle injectors (θ_spray = 70° and 60°) were examined and its results were compared with the results of conventional spray angle (θ_spray = 156°). In addition, to investigate the optimal operating conditions, early single-injection and multiple-injection strategies were employed to reduce cylinder wall-wetting of the injected fuels and to promote the ignition of premixed charge. The engine test was performed at 1400 rpm, and the injection timings were varied from TDC to BTDC 40° of the crank angle.The experimental results showed that the combustion pressure from single combustion for narrow-angle injectors (θ_spray = 70° and 60°) is increased, as compared to the results of the wide-angle injector (θ_spray = 156°) with advanced injection timing of BTDC 35°. In addition, two peaks of the rate of heat release (ROHR) are generated by the combustion of air-fuel premixed mixtures. DME combustion for all test injectors indicated low levels of soot emissions at all injection timings. The NO_x emissions for narrow-angle injectors simultaneously increased in proportion to the advance in injection timing up to BTDC 25°, whereas BTDC 20° for the wide-angle injector. For multiple injections, the combustion pressure and ROHR of the first injection with narrow-angle injectors are combusted more actively, and the ignition delay of the second injected fuel is shorter than with the wide-angle injector. However, the second combustion pressure and ROHR were lower than during the first injection, and combustion durations are prolonged, as compared to the wide-angle injector. With advanced timing of the first injection, narrow-angle injectors with multiple injections could achieve low NO_x levels and soot levels similar to single-injection cases.     

Electrochemical and infrared study of electro-oxidation of dimethyl ether (DME) on platinum polycrystalline electrode in acid solutions

Electro-oxidation of dimethyl ether (CH₃OCH₃, denoted as DME below) on Pt polycrystalline electrode has been investigated by electrochemical and in situ infrared (IR) measurements in acid solutions. A reaction intermediate species, (CH₃OCH₂-)_ad, has been observed in the low potential region as an initial product for dehydrogenation process of DME on Pt electrode surface. This species is subsequently decomposed to adsorbed carbon monoxide (CO) and finally oxidized to carbon dioxide (CO₂) in higher potential region. The time-resolved IR measurement is employed to follow the transient process of the formation and decomposition of the intermediate on Pt electrode surface. Based on these electrochemical and IR spectroscopic results, a reaction scheme for DME electro-oxidation process is proposed.     

Sulfonated poly(arylene ether sulfone) as an electrode binder for direct methanol fuel cell

Sulfonated poly(arylene ether sulfone) (sPAES) is synthesized and characterized for the application to the electrode binder for direct methanol fuel cell (DMFC). The effect of sPAES binder in the electrode on the cell performance is studied. The cell based on sPAES binder showed a good adhesion to the sPAES membrane, while Nafion binder is delaminated from the sPAES membrane after supplying the fuel for a prolonged time. The sPAES binder for electrode is found to be more efficient in achieving long-term stability of the cell performance than the conventional Nafion binder.     

Role of acidity on the hydrolysis of dimethyl ether (DME) to methanol

The activity of dimethyl ether (DME) hydrolysis was investigated over a series of solid acid and non-acid catalysts, zeolite Y [Si/Al = 2.5 and 15: denoted Y(Si/Al)], zeolite ZSM-5 [Si/Al = 15, 25, 40, and 140: denoted Z(Si/Al)], silica, zirconia, γ-alumina, and BASF K3-110 (commercial Cu/ZnO/Al₂O₃ catalyst). Dimethyl ether hydrolysis was carried out in an isothermal packed-bed reactor at ambient pressure.

Acid catalyzed dimethyl ether hydrolysis is equilibrium limited. All solid acid catalysts, with the exception of ZrO₂, attained equilibrium-limited conversions in the temperature range of interest (125–400 °C). Z(15), Z(25), and Z(40) reached equilibrium conversions at 200 °C, while Z(140), Y(15), and Y(2.5) reached equilibrium at 275 °C. γ-Alumina, the most active non-zeolite solid acid, attained equilibrium at 350 °C. Silica and BASF K3-110 were both ineffective in converting dimethyl ether to methanol. The observed activity trend for DME hydrolysis to methanol as a function of Si–Al ratio and catalyst type was:

     

Design framework for dimethyl ether (DME) production from coal and biomass-derived syngas via simulation approach

A comprehensive thermodynamic study was conducted to evaluate the comparative efficacy of methanol and dimethyl ether (DME) synthesis using CO₂ rich syngas feed. The first part of our study included assessing the relative performances of the methanol synthesis system, two step DME synthesis system, and one step DME synthesis system in terms of the CO_x conversion and product yield (methanol/DME) based on the Gibbs free energy minimization approach. The wide range of composition of CO₂-enriched syngas feed produced by the coal and biomass gasification was simulated using Aspen Plus and the following evaluation parameters were analyzed for a broad parameter range: reaction temperature (180–280°C), reaction pressure (10–80 bar), stoichiometry number (SN) (0–11), and CO₂/(CO₂ + CO) molar feed ratio (0–1) for isothermal as well as adiabatic conditions. Based on the equilibrium yield, one-step DME synthesis was discovered as the most viable process to utilize the co-gasification derived syngas effectively. In the second part of our study, the overall process efficiency was inspected through the process design of 1 tonnes per day (TPD) DME plant inclusive of heat integration, resulting in significant CO₂ abatement and DME production with high product purity and minimum energy consumption. Consequently, one-step DME production via CO₂-enriched syngas obtained through the coal or biomass gasification process is identified as the leading technology based on energy utilization and CO₂ abatement.     

Sulfonated poly(arylene ether sulfone) membranes based on biphenol for direct methanol fuel cells

A series of sulfonated poly(arylene ether sulfone) (PAES) were synthesized through direct aromatic nucleophilic substitution polycondensation of 3,3′-disulfonate-4,4′-dichlorodiphenylsulfone (SDCDPS), 4,4-dichlorodiphenylsulfone (DCDPS) and 4,4-biphenol (BP). With increasing sulfonate groups in the polymer, water uptake, ion exchange capacity (IEC) and proton conductivities increased, resulting from enhanced membrane hydrophilicity. The membranes exhibited higher thermal stability up to 300 °C, verified by thermogravimetric analysis (TGA). A maximum proton conductivity of 0.11 S/cm at 50 mol% of sulfonation degree was measured at 30 °C, which is slightly higher than Nafion®117 membrane (0.0908 S/cm). However, the methanol permeability of the PAES membrane was much lower than that of Nafion®117 membrane. As a result, a single cell performance test demonstrated that PAES-BP with 50 mol% sulfonation degree exhibited higher power density than Nafion®117.     

Influence of ambient flow conditions on the droplet atomization characteristics of dimethyl ether (DME)

This paper describes the effects of ambient flow conditions on the droplet atomization characteristics of dimethyl ether (DME) both experimentally and numerically.In this investigation, the droplet atomization of DME fuel affected by ambient flow conditions was studied in terms of droplet mean size and detected droplet percentage under elevated ambient pressures and temperatures. In order to predict the DME spray atomization, the hybrid breakup model combined with KH-RT (Kelvin-Helmholtz and Rayleigh-Taylor) and KH-DDB (Kelvin-Helmholtz and Drop Deformation Breakup) models was applied in this study.It was revealed that the spray arrival time of DME fuel under a high ambient pressure increased in accordance with the increase in ambient pressure in the spray chamber. It can be seen that more small droplets are distributed at high ambient flow pressure conditions than at atmospheric conditions. This is a consequence of enhanced atomization of DME fuel. On the other hand, when the ambient pressure increases to 2 MPa, the Sauter mean diameter (SMD) increases only slightly compared with that at 1 MPa of pressure. The SMD value of droplets is increased as ambient temperature is increased. Under the high temperature condition in the chamber, the small droplets of DME fuel evaporate quickly and mix with the ambient air. As a result, it promotes the air-fuel mixing in a combustion chamber.     

离子液体修饰磺化聚醚醚酮作为离子交换膜

通过NaBH₄还原磺化聚醚醚酮(SPEEK)得到羟基功能化的SPEEK后,采用酯化反应将离子液体1-羧甲基-3-甲基咪唑氯盐接枝到磺化聚醚醚酮上得到接枝聚合物。实验结果表明：离子液体修饰后的磺化聚醚醚酮离子交换膜吸水率和溶胀度降低,而导电率得到了显著提高。     

Poly(ether ether ketone) solutions suitable for microfiltration membrane preparation

Poly(ether ether ketone) shows high stability against chemical and physical agents but is poorly soluble in most common solvents. We tested new solvents to obtain concentrated solutions that we used to prepare microfiltration membranes by the phase‐inversion technique. The prepared membranes were tested by the filtration of oily emulsions, and their structure was studied with scanning electron microscopy. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2550–2555, 2001     

The catalyst layer containing sulfonated poly(ether ether ketone) as the electrode ionomer for polymer electrolyte fuel cells

The electrode ionomer is a key component of the catalyst layer and therefore the introduction of new electrode ionomer would have a significant effect on cell performance. To investigate the effect of sulfonated poly(ether ether ketone) (sPEEK) as the electrode ionomer, the catalyst layer was prepared using sPEEK ionomer and its physical properties such as pore structure and the hydrophobicity were examined. The electrochemical characteristics of the membrane and electrode assemblies employing sPEEK ionomer-based catalyst layer were also analyzed. Even though sPEEK ionomer-based catalyst layer showed lower ohmic resistance compared with Nafion ionomer-based catalyst layer, complete pore-filling of sPEEK into the primary pore caused reduction in reactive surface area of the catalyst and hindrance in gas transfer. In addition, the very low hydrophobicity of sPEEK ionomer-based catalyst layer deteriorated gas transfer due to an increased water flooding.     

Fluorenyl‐containing Quaternary Ammonium Poly(arylene ether sulfone)s for Anion Exchange Membrane Applications

A series of anion exchange membranes (AEM) based on block quaternary ammonium poly(arylene ether sulfone) (QA‐bPAES) were successfully synthesized from 9,9′‐bis(4‐hydroxyphenyl) fluorene, 4,4′‐(hexafluoroisopropylidene) diphenol and 4,4′‐difluorodiphenyl sulfone via block polymerization, chloromethylation, quaternization, alkalization and solution casting. Properties of the obtained QA‐bPAES membranes, including ion exchange capacity (IEC), water uptake, swelling ratios, methanol permeability and ion conductivity were investigated. The obtained QA‐bPAES membranes showed low water uptakes, high ion conductivities and good physical and chemical stability. For example, the membrane of QA‐bPAES(20/10)‐1.34 with IEC of 1.34 mmol g⁻¹ exhibited swelling ratios of 5.0% and 5.1% in in‐plane and through‐plane direction, respectively, and ion conductivity of 15.6 mS cm⁻¹ in water at 60 °C with low methanol permeability of 1.06 × 10⁻⁷ cm² s⁻¹ (25 °C). All the results indicated that this type of block membranes had good potentials for alkaline anion exchange membrane fuel cell applications.     

Investigation on the fuel spray and emission reduction characteristics for dimethyl ether (DME) fueled multi-cylinder diesel engine with common-rail injection system

The aim of this study is to investigate the effects of dimethyl ether (DME) fuel on the engine performance and the exhaust emission reduction characteristics in a DME fueled four-cylinder diesel engine with a common rail injection system, as well as an injection characteristics and a spray behavior. The injection rate meter and the spray visualization system are utilized for the analysis of the injection characteristics and the spray behavior. Also, the modified four-cylinder diesel engine with 1.6 liter engine size is used for the investigation of the engine performance and the exhaust emission reduction characteristics of DME fuel.Based on the experimental investigation, it revealed that the injection quantity of DME fuel was larger than that of the ultra low sulfur diesel (ULSD) due to the high return fuel pressure at the same injection pressure and energizing duration. In this case, the injection quantity of DME fuel is increased by extension of real injection duration due to return fuel pressure.In combustion characteristics, the peak combustion pressure and the ignition delay of DME fuel are higher and faster than those of ULSD, respectively. The NO_x emission of DME fuel shows slightly higher than that of ULSD at the same engine load condition, and the soot emission of DME fuel is nearly zero level. The oxygenated component and volatility of DME resulted in HC and CO emissions that were lower than those of diesel.     

Sulfonated poly(ether ether sulfone) copolymers for proton exchange membrane fuel cells

Novel aromatic sulfonated poly(ether ether sulfone)s (SPEESs) with tert‐butyl groups were synthesized by aromatic nucleophilic polycondensation of disodium 3,3′‐disulfonate‐4,4′‐dichlorodiphenylsulfone (SDCDPS), 4,4′‐dichlorodiphenylsulfone (DCDPS), and tert‐butylhydroquinone (TBHQ). The resulting copolymers showed very good thermal stability and could be cast into tough membranes. The morphology of the membranes was investigated with atomic force microscopy. The proton conductivity of SPEES‐40 membranes increased from 0.062 S/cm at 25°C to 0.083 S/cm at 80°C, which was higher than the 0.077 S/cm of Nafion 117 under the same testing conditions. These copolymers are good candidates to be new polymeric electrolyte materials for proton exchange membrane fuel cells. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1443–1450, 2007     

Influence of silica content in sulfonated poly(arylene ether ether ketone ketone) (SPAEEKK) hybrid membranes on properties for fuel cell application

Sulfonated poly(arylene ether ether ketone ketone) (SPAEEKK) copolymer containing pendant sulfonic acid group (sulfonic acid content (SC) = 0.67) was synthesized from commercially available monomers such as sodium 6,7-dihydroxy-2-naphthalenesulfonate (DHNS), 1,3-bis(4-fluorobenzoyl)-benzene (BFBB), and hexafluorobisphenol A (6F-BPA). SPAEEKK/silica hybrid membranes were prepared using the sol-gel process under acidic conditions. The SPAEEKK/silica hybrid membranes were fabricated with different silica contents and the membranes were modified to achieve improved proton conductivity incorporating P-OH groups (H₃PO₄ treatment).The silica particles within the membranes were used for the purpose of blocking excessive methanol cross-over and for forming a pathway for proton transport due to water absorption onto the hydrophilic SiOH surface. The proton conductivities of H₃PO₄-doped membranes were somewhat higher than the un-doped (H₃PO₄-free) membranes due to increasing hydrophilicity of the membranes. The presence of silica particles within the organic polymer matrix, which decreases the ratio of free water to bound water due to the SiOH on the surface of silica derived from sol-gel reaction, results in hybrid membranes with reduced methanol permeability and improved proton conductivity.     

Sulphonated Poly(ether ether ketone) Proton Exchange Membranes for Fuel Cell Applications

Polymer electrolyte membrane fuel cells (PEMFCs) are promising new power sources for automotive and portable devices. Nafion® is the currently used membrane in PEMFCs. Although these membranes show high proton conductivity and excellent chemical stability, their high cost makes them unpractical for commercial purposes. Sulphonated poly(ether ether ketone) (SPEEK) ionomers were synthesized using chlorosulphonic acid as the sulphonating agent in dichloromethane medium. Homogeneous proton-conducting membranes were developed from the obtained SPEEK by solvent casting method. Membranes were assessed for their suitability in fuel cell applications. The extent of sulphonation was controlled by varying the reaction time, concentration of polymer, and concentration of sulphonating agent. The SPEEK membranes exhibit degree of sulphonation from 10 to 66%, ion exchange capacity from 0.29 to 1.92 meq/g and maximum water and methanol uptake up to 54 and 22%, respectively, at 25°C. The membranes were characterized by FTIR to confirm sulphonation, and DSC and TGA to investigate the thermal stability. The proton conductivities of such membranes were found to be excellent in the order of 10^?2 S/cm in the fully hydrated condition at room temperature as measured by impedance spectroscopy. The durability of the membranes was also tested. The study revealed the possibility of a cheaper alternative membrane for use in PEMFC.