替代燃料二甲醚的燃烧特性及其污染物甲醛的生成消耗机理研究

化石燃料的不可再生性决定了其不能长久为全球经济和科技的发展提供能源动力，从可持续发展和能源战略的角度考虑，能够替代石油及其衍生品的清洁替代燃料研究已经成为提高能源供应安全、改善环境污染问题、应对气候变化的重要措施，对替代燃料的研究和应用已经成为各方关注和开发的热点。 二甲醚(DME、CH3OCH3)是一种最简单的醚类，它不含C-C健，可以由天然气、煤、生物质燃料等大量制备，而且具有较高的辛烷值(55-60)，较低的碳氢化合物、CO排放，没有PM排放，因而被认为是一种非常有发展前景的发动机替代燃料，已经受到了广泛的关注。但是，在发动机燃用DME的实验研究表明，在其排气中有非常规污染物甲醛(HCHO)、乙醛(CH3CHO)，甲酸甲酯(HCOOCH3)等排放，这些有机污染物会对环境和人类健康产生严重的危害，在环保要求日益严格的趋势下，这就制约了二甲醚的规模化应用。因此，对二甲醚燃烧性能、氧化中间产物甲醛等的产生和排放机理、相关污染物抑制技术需要进行着重研究，这对二甲醚燃料规模化应用、相关二甲醚燃烧器设计、燃烧性能的优化以及污染物控制技术的研究等都有着重要的理论指导意义和参考价值。 为了充分理解二甲醚燃料的燃烧特性、非常规污染物甲醛的产生和消耗机理，本文以实验和二甲醚化学反应动力学机理为指导，对二甲醚预混燃烧的燃烧特性、相关污染物和甲醛产生和消耗的机理做了详细的研究；并针对二甲醚燃料的不同应用背景，对二甲醚燃料低温下的氧化和甲醛生成特性、DME与LPG掺混燃烧特性和甲醛生成消耗机理进行了深入的研究，具体工作有： 研究了二甲醚预混燃烧特性、火焰中甲醛等污染物的产生特性，建立了火焰中甲醛取样、测量的方法和实验平台。并对当量比和燃料流量对二甲醚预混燃烧的燃烧特性、甲醛生成特性影响进行了考察，实验结果表明二甲醚是一种优良的替代燃料，在二甲醚火焰中甲醛是其重要的中间产物，甲醛浓度分布与当量比和预混气流速密切相关。当量比一定时，随着预混气流速的增加，火焰中甲醛产生的范围变窄，且甲醛浓度峰值逐渐移向燃烧器出口，而甲醛产生的浓度峰值数值上相差不大，甲醛在形成峰值后被快速消耗，其浓度在0.1mm内下降到几乎为零；在二甲醚流量一定时，随着当量比的增加，火焰中产生了更多的甲醛，火焰中甲醛分布的范围也变宽，而且当量比越大，甲醛的消耗也变缓，在当量比为0.8时，甲醛浓度从峰值到被消耗距离变为2mm，远大于当量比0.6和0.7下0.1mm的消耗距离。 对二甲醚预混燃烧进行数值研究和化学动力反应机理分析后发现，在二甲醚燃烧中，二甲醚的氧化反应途径主要是通过脱氢生成CH3OCH2和在高温下的直接裂解反应而进行，其中脱氢反应是低温下二甲醚消耗的主要途径，而在高温反应阶段(T>1000K)，DME的直接裂解和燃料的脱氢反应共同起主导作用；非常规污染物甲醛通过DME脱氢产物CH3OCH2的裂解和外部氧化而生成，在高温时通过DME直接裂解后被氧化产生；甲醛的消耗反应则是通过与H、O、OH和CH3基的氧化反应而完成，其中与O、OH基的反应在燃烧中起主要作用。因此二甲醚燃烧中甲醛的抑制关键在燃烧中甲醛的消耗阶段，采取有效的技术措施，如优化燃烧器结构提高二甲醚燃烧室内的温度、在燃烧区保证充足的氧气供应等措施，加快甲醛的消耗速度以促进其被完全氧化，可以实现二甲醚燃烧中甲醛的零排放。 针对柴油发动机燃用DME燃料时，燃料在燃烧室停留时间过短，造成部分未燃二甲醚随尾气排放，对DME在低温下(<800K)的氧化特性和甲醛生成特性进行了实验研究。结果表明，二甲醚在200℃左右就开始发生氧化反应，在200~400℃温度范围内被氧化而生成大量中间产物甲醛，且在此温度范围内甲醛不易被氧化分解，而发动机尾气温度（一般在200~600℃之间）处于甲醛最易生成的范围，因此未燃二甲醚在尾气中发生低温氧化反应生成的甲醛，是发动机燃用DME而排放高浓度甲醛的重要来源。研究结论为柴油发动机燃用DME抑制非常规污染物甲醛的排放提供了新的参考。 DME作为替代燃料，部分替代及与其他石化系燃料掺混燃烧是目前的重要应用方向，对DME与LPG掺混燃烧特性和甲醛生成特性进行了实验研究，结果表明，在DME与LPG掺混燃烧中，固定当量比和燃料质量流量的条件下，两种燃料存在一个最佳掺混比，在此掺混比例下，混合燃料着火提前，燃料燃烧性能最佳；DME与LPG混合燃料中，二甲醚是燃烧中甲醛产生的主要来源，控制DME的完全氧化和燃烧是抑制DME与LPG掺混燃烧排放甲醛的主要途径，这为更好地应用DME与LPG混合燃料提供了参考。 能否清洁高效燃烧是决定替代燃料DME应用规模和途径中的关键任务，本文对DME燃烧特性、非常规污染物甲醛的生成排放特性、低温下DME的氧化特性、DME与LPG掺混燃烧特性的研究，从不用的应用方向和领域对DME清洁高效燃烧进行了探讨和研究，研究成果可以为清洁高效利用二甲醚、抑制甲醛排放，以及开发相关燃烧技术、燃烧器提供实验依据和理论指导。本文在DME燃烧特性和非常规污染物甲醛的产生与排放方面取得了具有创新性的研究结果。

A novel combustion process for the synthesis of fine particle α-alumina and related oxide materials

Synthesis of fine particle α-alumina and related oxide materials such as MgAl2O4, CaAl2O4, Y3Al5O12 (YAG), Image , β′-alumina, LaAlO3 and ruby powder (Image ) has been achieved at low temperatures (500°C) by the combustion of corresponding metal nitrate-urea mixtures. Solid combustion products have been identified by their characteristic X-ray diffraction patterns. The fine particle nature of α-alumina and related oxide materials has been investigated using SEM, TEM, particle size analysis and surface area measurements.

Rocket Propellant Combustion Studies in a Constant Volume Bomb

A constant volume window bomb has been used to measure the characteristic velocity (c*) of rocket propellants. Analysis of the combustion process inside the bomb including heat losses has been made. The experiments on double base and composite propellants have revealed some (i) basic heat transfer aspects inside the bomb and (ii) combustion characteristics of Ammonium Perchlorate-Polyester propellants. It has been found that combustion continues even beyond the peak pressure and temperature points. Lithium Fluoride mixed propellants do not seem to indicate significant differences in c*) though the low pressure deflagration limit is increased with percentage of Lithium Fluoride.

Effect of Li+-ion on enhancement of photoluminescence in Gd2O3:Eu3+ nanophosphors prepared by combustion technique

Gd2O3:Eu3+ (4 mol%) nanophosphor co-doped with Li+ ions have been synthesized by low-temperature solution combustion technique in a short time. Powder X-ray diffractometer (PXRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), UV-VIS and photoluminescence (PL) techniques have been employed to characterize the synthesized nanoparticles. It is found that the lattice of Gd2O3:Eu3+ phosphor transforms from monoclinic to cubic as the Li+-ions are doped. Upon 254 nm excitation, the phosphor showed characteristic luminescence D-5(0) -> F-7(J) (J= 0-4) of the Eu3+ ions. The electronic transition located at 626 nm (D-5(0) -> F-7(2)) of Eu3+ ions was stronger than the magnetic dipole transition located at 595 nm (D-5(0) -> F-7(1)). Furthermore, the effects of the Li+ co-doping as well as calcinations temperature on the PL properties have been studied. The results show that incorporation of Li+ ions in Gd2O3:Eu3+ lattice could induce a remarkable improvement of their PL intensity. The emission intensity was observed to be enhanced four times than that of with out Li+-doped Gd2O3:Eu3+. (C) 2010 Elsevier B.V. All rights reserved,

Structural, optical and EPR studies on ZnO:Cu nanopowders prepared via low temperature solution combustion synthesis

Cu (0.1 mol%) doped ZnO nanopowders have been successfully synthesized by a wet chemical method at a relatively low temperature (300 degrees C). Powder X-ray diffraction (PXRD) analysis, scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier transformed infrared (FTIR) spectroscopy, UV-Visible spectroscopy, Photoluminescence (PL) and Electron Paramagnetic Resonance (EPR) measurements were used for characterization. PXRD results confirm that the nanopowders exhibit hexagonal wurtzite structure of ZnO without any secondary phase. The particle size of as-formed product has been calculated by Williamson-Hall (W-H) plots and Scherrer's formula is found to be in the range of similar to 40 nm. TEM image confirms the nano size crystalline nature of Cu doped ZnO. SEM micrographs of undoped and Cu doped ZnO show highly porous with large voids. UV-Vis spectrum showed a red shift in the absorption edge in Cu doped ZnO. PL spectra show prominent peaks corresponding to near band edge UV emission and defect related green emission in the visible region at room temperature and their possible mechanisms have been discussed. The EPR spectrum exhibits a broad resonance signal at g similar to 2.049, and two narrow resonances one at g similar to 1.990 and other at g similar to 1.950. The broad resonance signal at g similar to 2.049 is a characteristic of Cu2+ ion whereas the signal at g similar to 1.990 and g similar to 1.950 can be attributed to ionized oxygen vacancies and shallow donors respectively. The spin concentration (N) and paramagnetic susceptibility (X) have been evaluated and discussed. (C) 2011 Elsevier B. V. All rights reserved.

Combustion synthesis and properties of Ce1-xPrxO2-delta red ceramic pigments

Praseodymium-doped ceria red pigments, Ce1−xPrxO2−δ, x=0–0.5 have been prepared by the thermal decomposition of the redox compound Ce1−xPrx(N2H3COO)3·3H2O as well as by the combustion of aqueous solutions containing cerous nitrate, praseodymium nitrate and oxalyl dihydrazide (ODH)/ammonium acetate. Formation of the pigment has been confirmed by its characteristic red colour and reflectance spectra which shows the reflection edge not, vert, similar690 nm corresponding to charge transfer from the ligand orbitals to the localised 4f1 of Pr4+. The particulate properties of praseodymium-doped ceria pigments obtained from the combustion of redox compounds and redox mixtures are compared.

Combustion synthesis, characterization and Raman studies of ZnO nanopowders

Spherical shaped ZnO nanopowders (14-50 nm) were synthesized by a low temperature solution combustion method in a short time <5 min. Rietveld analysis show that ZnO has hexagonal wurtzite structure with lattice constants a = 3.2511(1) angstrom, c = 5.2076(2) angstrom, unit cell volume (V) = 47.66(5) (angstrom)(3) and belongs to space group P63mc. SEM micrographs reveal that the particles are spherical in shape and the powders contained several voids and pores. TEM results also confirm spherical shape, with average particle size of 14-50 nm. The values are consistent with the grain sizes measured from Scherrer's method and Williamson-Hall (W-H) plots. A broad UV-vis absorption spectrum was observed at similar to 375 nm which is a characteristic band for the wurtzite hexagonal pure ZnO. The optical energy band gap of 3.24 eV was observed for nanopowder which is slightly lower than that of the bulk ZnO (3.37 eV). The observed Raman peaks at 438 and 588 cm(-1) were attributed to the E(2) (high) and E(1) (LO) modes respectively. The broad band at 564 cm(-1) is due to disorder-activated Raman scattering for the A(1) mode. These bands are associated with the first-order Raman active modes of the ZnO phase. The weak bands observed in the range 750-1000 cm(-1) are due to small defects. (C) 2011 Elsevier B.V. All rights reserved.

Self propagating combustion synthesis and luminescent properties of nanocrystalline CeO2: Tb3+ (1-10 mol%) phosphors

Undoped and Tb3+ (1-10 mol%) doped CeO2 nanophosphors were synthesized by low temperature solution combustion method. The combustion derived products were well studied by Powder X-ray diffraction (PXRD), Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and Ultraviolet visible (UV-Vis) characterizations. The thermoluminescence (TL) glow curves of CeO2: Tb3+ (1-10 mol%) nanophosphors exposed to c source (60Co) for various doses were discussed for the first time. Two TL glow peaks recorded at 182 and 262 degrees C respectively. The TL intensity at 262 degrees C peak increases linearly in the dose range 0.5-7 kGy. Further, this peak was well defined, intense and glow peak structure does not change with c-dose as a result, it was quite useful in TL dosimetry of ionizing radiations. The kinetic parameters associated with the glow peak were estimated using Chen's half width method. The photoluminescence emission (PLE) spectra consists of characteristic peaks at 544 and 655 nm which were attributed to D-5(4) -> F-7(5) and D-5(4) -> F-7(2) transitions of Tb3+ ions. The optimal concentration of Tb3+ ions was found to be 7 mol%. The color co-ordinates of CeO2: Tb3+ (1-10 mol%) located in green region. Hence, this phosphor was quite useful for display applications. (C) 2013 Elsevier B. V. All rights reserved.

Experimental studies on self-ignition of hydrogen/air supersonic combustion

Self-ignition tests of a model scramjet combustor were conducted by using parallel sonic injection of gaseous hydrogen from the base of a blade-like strut into a supersonic airstream, The vitiated air was produced by burning H-2, O-2, and air to a stagnation temperature of 1000-2100 K and a stagnation pressure of 0.8-1.6 MPa, The effects of different parameters on the self-ignition limits were analyzed, In addition, the effects of the combustor's different wall configurations on self-ignition limits were specifically studied. It was found that the wall configurations of the combustor had a significant effect on self-ignition limits, which might have variations of 420-840 K deg in stagnation temperature; however, the local static temperature in the recirculation zones for different wall configurations remained the same at approximately 1100 K, It was found that self-ignition could initiate at the exit of the combustor and this can be considered as a weak self-ignition characteristic.

Coflow jets with large velocity difference - a new aerodynamic principle of flame stabilization and combustion intensification

A new aerodynamic principle of flame stabilization and combustion intensification, the coflow jets with large velocity difference, is described. One or more small high-velocity jets of air or steam, injected off the axis and in the same direction as the low-velocity main fuel-air flow into the combustor, create a large recirculation zone of high turbulence intensity in which the combustibles and high temperature gases are effectively mixed, so that stable and intensive combustion can be maintained even for fuels with poor ignition. A pulverized coal combustor based on the principle mentioned above is shown to be characteristic of excellent combustoom and a simple structure. A number of precombustors of this type are in operation at some power stations and industrial boilers of China. Using such precombustor, successtul startups and part-load operation of the boilers have become available under conditions of unpreheated air and low-grade coal with volatiles as low as 15% and ash content as high as 30%. This principle shows good promise as an attractive new technology of combustion.

Modal dynamics of self-excited azimuthal instabilities in an annular combustion chamber

In this paper we describe the time-varying amplitude and its relation to the global heat release rate of self-excited azimuthal instabilities in a simple annular combustor operating under atmospheric conditions. The combustor was modular in construction consisting of either 12, 15 or 18 equally spaced premixed bluff-body flames around a fixed circumference, enabling the effect of large-scale interactions between adjacent flames to be investigated. High-speed OH* chemiluminescence imaged from above the annulus and pressure measurements obtained at multiple locations around the annulus revealed that the limit cycles of the modes are degenerate in so much as they undergo continuous transitions between standing and spinning modes in both clockwise (CW) and anti-clockwise (ACW) directions but with the same resonant frequency. Similar behaviour has been observed in LES simulations which suggests that degenerate modes may be a characteristic feature of self-excited azimuthal instabilities in annular combustion chambers. By modelling the instabilities as two acoustic waves of time-varying amplitude travelling in opposite directions we demonstrate that there is a statistical prevalence for either standing m=1 or spinning m=±1 modes depending on flame spacing, equivalence ratio, and swirl configuration. Phase-averaged OH* chemiluminescence revealed a possible mechanism that drives the direction of the spinning modes under limit-cycle conditions for configurations with uniform swirl. By dividing the annulus into inner and outer annular regions it was found that the spin direction coincided with changes in the spatial distribution of the peak heat release rate relative to the direction of the bulk swirl induced along the annular walls. For standing wave modes it is shown that the globally integrated fluctuations in heat release rate vary in magnitude along the acoustic mode shape with negligible contributions at the pressure nodes and maximum contributions at the pressure anti-nodes. © 2013.

A flame surface density approach to large-eddy simulation of premixed turbulent combustion

The flame surface density approach to the modeling of premixed turbulent combustion is well established in the context of Reynolds-averaged simulations. For the future, it is necessary to consider large-eddy simulation (LES), which is likely to offer major advantages in terms of physical accuracy, particularly for unsteady combustion problems. LES relies on spatial filtering for the removal of unresolved phenomena whose characteristic length scales are smaller than the computational grid scale. Thus, there is a need for soundly based physical modeling at the subgrid scales. The aim of this paper is to explore the usefulness of the flame surface density concept as a basis for LES modeling of premixed turbulent combustion. A transport equation for the filtered flame surface density is presented, and models are proposed for unclosed terms. Comparison with Reynolds-averaged modeling is shown to reveal some interesting similarities and differences. These were exploited together with known physics and statistical results from experiment and from direct numerical stimulation in order to gain insight and refine the modeling. The model has been implemented in a combustion LES code together with standard models for scalar and momentum transport. Computational results were obtained for a simple three-dimensional flame propagation test problem, and the relative importance of contributing terms in the modeled equation for flame surface density was assessed. Straining and curvature are shown to have a major influence at both the resolved and subgrid levels.

Investigation on combustion derived BaMgAl10O17:Eu2+ phosphor powder and its corresponding PVP/BaMgAl10O17:Eu2+ nanocomposite

This work focuses on the study of BaMgAl10O17:Eu2+ (BAM:Eu) nanophosphors prepared by a microwave-assisted combustion procedure and more especially on the polymer/BAM:Eu nanocomposite film suitable for optical devices such as solid-state-lighting. Powder presented a specific nanomorphology, highly friable and thus easily ground into fine particles. They were then homogeneously dispersed into a polymer solution (poly(N-vinylpyrrolidone) or PVP) to elaborate a polymer phosphor nanocomposite. The structural, morphological and optical features of the nanocomposite film have been studied and compared to those of a pristine PVP film and BAM:Eu powder. All the characterizations (XRD, SEM, SAXS, etc.) proved that the blue phosphor nanoparticles are well incorporated into the polymer nanocomposite film which exhibited the characteristic blue emission of Eu2+ under UV light excitation. Furthermore, the photostability of the polymer/phosphor nanocomposite film has been studied after exposure to accelerated artificial photoageing at wavelengths above 300 nm.

Photoelectroactivity of Bismuth Vanadate Prepared by Combustion Synthesis: Effect of Different Fuels and Surfactants

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)