高碱煤燃烧过程中灰中主要元素的迁移规律

针对我国新疆高碱煤燃烧过程中的强沾污、结渣特性,对某300MW亚临界高碱煤锅炉炉内各受热面的沾污灰样进行了XRF和SEM-EDX分析.结果表明:在800~1 100℃烟气温度区间内,灰样中CaO、MgO和SO3的质量分数较高;当烟气温度降低至600~800℃时,灰样中Na2O、Fe2O3和SO3的质量分数较高,Na2SO4、CaSO4和NaFeSO4等物质是导致高碱煤燃烧过程中高温对流受热面发生严重沾污的主要原因;669~915℃烟气温度区间内的灰样发生初始熔融的温度及其所对应的液相质量分数要高于其他部位的灰样;灰样C颗粒表面附着粒径为2~4μm的富含Na、S的Na2SO4等颗粒,而钠的硫酸盐在高温下具有较高的黏性和较低的熔点,这是导致该温度下发生严重沾污的主要原因之一.     

温度对煤化工废焦积灰特性的影响

为了得到温度对煤化工废焦燃用过程积灰特性的影响机制,在高温沉降炉实验系统上研究了烟气温度和壁面温度对热解废焦初始层及烧结层沉积灰理化特性的影响。结果表明:烟气温度主要影响烧结层沉积灰的理化特性,对初始层沉积灰理化特性的影响较小,而壁面温度对沉积灰理化特性的影响与之相反;随着烟气温度的降低,沉积灰的熔融粘连情况逐渐减弱,通过吹灰或振打方式较易被清除,随着壁面温度的降低,初始层沉积灰的熔融程度降低,对大颗粒的捕捉行为减弱,也在一定程度上减轻了飞灰沉积;碱金属多以异相凝结的方式存在于初始层沉积灰中,烧结层沉积灰中碱金属含量较少;高钙和高铁特性是导致该燃料在燃烧利用过程中受热面积灰严重的主要原因。     

生物质灰熔融温度预测模型的研究

基于生物质灰成分和熔融温度实测数据构成的数据样本分析了灰成分对灰熔融性的影响,采用回归分析方法建立了灰熔融温度预测模型,并对回归方程的显著性及准确性进行了检验.结果表明:SiO2、CaO、K2O、SO3和P2O5对生物质灰熔融性的影响具有双重性;MgO和Na2O对生物质灰起助熔作用;该预测模型适用于预测生物质灰熔融温度,具有工程应用价值.     

气化条件下混煤灰熔融特性及矿物质演变规律

通过实验研究了高温气化条件下混煤灰的熔融特性及矿物质演变规律.结果表明,气化条件下混煤灰熔融温度的变化规律并不与配煤比例成线性关系,而与相应三元相图的液相线温度具有良好的相似性;随着低灰熔点煤灰的加入,混煤灰在三元相图上的位置逐渐由莫来石结晶区向钙长石结晶区移动,并在二元共晶线或三元共晶点附近熔融温度的变化最为显著,且低于周围位置的熔融温度;由于低灰熔点煤灰中含有较多的硬石膏、辉石、长石等矿物,高温气化条件下能分解成CaO、FeO等助熔矿物,这些助熔矿物能够与高灰熔点煤灰中的莫来石、石英等发生反应生成钙长石、铁橄榄石等低熔融矿物,从而降低了高灰熔点煤灰的熔融温度.     

FactSage软件应用于预测煤灰熔融流动温度

利用FactSage软件绘制了煤灰主要组分的三元相图,从热力学角度预测及分析了煤灰熔融性与流动性,表明煤灰液相线温度与灰熔融流动温度间确实存在对应关系。借助FactSage软件模拟计算煤灰熔融过程中生成的矿物质各相态组成,得出煤灰在该温度下的熔融矿物液固比率。对比实验测量值与软件计算值,结果表明当熔融渣中液含率为90wt%时对应的温度值与其灰熔融流动温度值最接近,并且FactSage软件同样也适用于预测高灰熔点煤助熔剂CaO的添加量。     

灰粘熔排渣技术在内循环流化床垃圾焚烧中的应用

提出将粘熔排渣技术应用于内循环流化床垃圾焚烧处理.从垃圾灰渣化学组分等角度分析其必要性和可行性.采用树脂颗粒作为床料,微晶蜡颗粒为低熔点物质,在非均匀布风内循环流化床内进行热态团聚模拟试验.试验表明：床内温度分区、团聚过程区域化是灰粘熔排渣技术的重要保证,内循环颗粒流动有利于排渣顺利进行,缩短粘性物质在床内的停留时间.图4表1参15     

藻类和木质生物质与烟煤掺混燃烧结渣特性

文章利用沉降炉系统开展了河南烟煤与海草和桃木两种生物质的混燃成渣特性实验,对混燃灰的理化性能、矿物质转化过程及其聚集成渣的趋势进行了研究。研究结果表明:藻类生物质海草能够加剧混燃灰渣颗粒的聚集成块趋势,而木本生物质桃木仅造成混燃灰颗粒粒径的略微增长;掺混海草导致混燃灰中的碱金属,Cl和S元素含量增加,灰渣中出现大量低熔点的长石和类长石矿物质,从而增强了灰渣的黏附能力,表现为由包覆引起的成渣机制;掺混桃木的混燃灰因含有较高的Ca和Fe等元素,从而生成了较多的能够抑制低温共熔物形成的钙质硅(铝)酸盐,其提高了混燃灰的熔融温度,并减缓了成渣趋势;藻类生物质中的碱金属,Cl和S等元素除对成渣过程有较大影响外,还会引起冷凝腐蚀等问题,从而对其资源化应用产生负面影响。     

灰特性对燃煤炉内灰沉积行为的影响

为了解灰特性对燃煤炉内灰沉积行为的影响,以黄陵、神木和新汶3种具有不同灰特性的燃煤为研究对象,通过自制灰污热流探针和SiC结渣棒,分别模拟了正常情况及存在烟气冲墙贴壁情况下的锅炉受热面灰沉积行为,比较了灰渣外形、化学成分、熔融温度和热流变化率等特性参数,并通过对灰渣样晶的X-射线衍射、扫描电镜及能谱分析,获得了3种燃煤灰沉积物的元素组成、矿物相及微观结构和形貌特征.结果表明,由于Ca、Fe的协同作用,黄陵煤的灰沉积特性强于神木和新汶煤,Ca、Fe是引起这类煤灰沉积的主要矿物元素,硬石膏、钙长石和赤铁矿是灰沉积物中的主要矿物相;当存在烟气冲墙贴壁时,灰沉积物中Fe含量很高.使熔融温度大大降低,从而加剧受热面的灰沉积过程,在工程实际中应采取相应措施,避免出现这种情况.     

应用计算机控制系统预防危险废物回转窑焚烧结渣的研究

危险废物回转窑焚烧处置工艺具有诸多优点,但是当危险废物焚烧产生的灰渣熔融温度较低时,窑内的高温气氛会将灰渣颗粒熔融成液相,导致回转窑的结渣。灰渣的熔融实验结果证明,灰渣的熔融温度比较低,变形温度仅有1000℃左右。化学组分对灰渣熔融温度的影响研究表明,SiO2、Al2O3、CaO和CaSO4都对灰渣的熔融温度起到了升高的作用。采用计算机控制系统对整个系统进行监测、控制和管理,控制回转窑的温度在略低于灰渣熔融温度的水平运行,或者对危险废物在焚烧前进行合理的预混配伍,都能起到较好的预防回转窑结渣的作用。     

XAFS法研究煤灰熔融过程中Fe元素形态的变化

采用上海同步辐射光源X射线吸收精细结构谱对还原性气氛下高灰熔点和低灰熔点煤灰样的熔融过程进行了观察.结果表明:煤灰熔融过程中Fe的价态形式由Fe3+向Fe2+转变;高灰熔点煤灰样在熔融过程中Fe的价态变化大多发生在900~1 300℃的温度段,Fe由四面体配位向八面体配位转变;低灰熔点煤灰样熔融时,一部分Fe首先形成四面体配位,然后再向八面体配位转变;Fe元素的这些形态变化在熔融过程开始之前就已经发生;低灰熔点煤灰样在熔融过程中第1层配位Fe—O结构发生了明显变化,而且只发生在完全熔融时刻,而高灰熔点煤灰样则没有明显观察到此配位结构的变化.     

Optical properties and thermal stability of pulsed-sputter-deposited AlxOy/Al/AlxOy multilayer absorber coatings

Spectrally selective Al_xO_y/Al/Al_xO_y multilayer absorber coatings were deposited on copper (Cu) and molybdenum (Mo) substrates using a pulsed sputtering system. The Al targets were sputtered using asymmetric bipolar-pulsed DC generators in Ar+O₂ and Ar plasmas to deposit an Al_xO_y/Al/Al_xO_y coating. The compositions and thicknesses of the individual component layers were optimized to achieve high solar absorptance (α=0.950-0.970) and low thermal emittance (ε=0.05-0.08). The X-ray diffraction data in thin film mode showed an amorphous structure of the Al_xO_y/Al/Al_xO_y coating. The X-ray photoelectron spectroscopy data of the Al_xO_y/Al/Al_xO_y multilayer absorber indicated that the Al_xO_y layers present in the coating were non-stoichiometric. The optical constants (n and k) of the multilayer absorber were determined from the spectroscopic ellipsometric data. Drude's free-electron model was used for generating the theoretical dispersion of optical constants for Al films, while the Tauc-Lorentz model was used for modeling optical properties of the dielectric Al_xO_y layers. In order to study the thermal stability of the Al_xO_y/Al/Al_xO_y coatings, they were subjected to heat treatment (in air and vacuum) at different temperatures and durations. The multilayer absorber deposited on Cu substrates exhibited high solar selectivity (α/ε) of 0.901/0.06 even after heat-treatment in air up to 400 °C for 2 h. At 450 °C, the solar selectivity decreased significantly on Cu substrates (e.g., α/ε=0.790/0.07). The coatings deposited on Mo substrates were thermally stable up to 800 °C in vacuum with a solar selectivity of 0.934/0.05. The structural stability of the absorber coatings heat treated in air (up to 400 °C) and vacuum (up to 800 °C) was confirmed by micro-Raman spectroscopy measurements. Studies on the accelerated aging tests suggested that the absorber coatings on Cu were stable in air up to 75 h at 300 °C and the service lifetime of the multilayer absorber was predicted to be more than 25 years. Further, the activation energy for the degradation of the multilayer absorber heat treated for longer durations in air is of the order of 64 kJ/mol.     

Hydrogen storage properties of multi-principal-component CoFeMnTixVyZrz alloys

This study presents an innovative multi-principal-element CoFeMnTiVZr alloy system for the absorption and desorption of hydrogen. Pressure-composition-isotherms (PCIs) demonstrate that CoFeMnTi_xVZr, CoFeMnTiV_yZr, and CoFeMnTiVZr_z can absorb and desorb hydrogen for x, y, and z that satisfy 0.5 ≤ x ≤ 2.5, 0.4 ≤ y ≤ 3.0, and 0.4 ≤ z ≤ 3.0, respectively. X-ray diffraction (XRD) reveals that CoFeMnTi_xV_yZr_z alloys have a simple C14 Laves phase with a single set of lattice parameters before and after PCI tests. The distributions of each element in CoFeMnTi_xV_yZr_z alloys are roughly equal, as revealed by SEM/EDS mapping. The effects of values x, y, and z on the hydrogen storage properties are elucidated in terms of lattice constant, element segregation, hydride formation enthalpies of the alloy components and hydrogen, and the averaged formation enthalpy. The high-entropy effect promotes the formation of a single C14 Laves phase, and the maximum hydrogen storage capacity is strongly related to the hydride formation enthalpy of the alloy and hydrogen.     

C/H/O/N/S/Cl/K/Na元素的详细化学反应机理的简化与验证

基于Senkin模型,应用自编化学反应机理简化程序,结合Kinalc和Mechmod开源程序,发展了详细化学反应机理的简化与验证方法.以电站锅炉燃烧的计算流体力学(CFD)数值模拟为应用背景,建立了考虑C/H/O/N/S/Cl/K/Na元素的详细化学反应机理(115组分,1,342基元反应),并运用此方法得到简化反应机理(28组分,20反应).验证结果表明,该简化机理在锅炉运行的主要参数变化范围内(温度T=1,100～1,500,℃,过量空气系数λ=0.8～1.2)具有较好的准确性和较高的计算效率,可应用于锅炉燃烧的CFD计算.     

Electrochromic properties of NiOxHy thin films

NiO_xH_y films were prepared by DC magnetron sputtering in H₂/O₂ atmosphere. NiO_xH_y coatings with transparency and high electrochromic efficiency were obtained by changing H₂ content. A 60 nm thick NiO_xH_y film with transmittance of 0.57 (as-deposited state), 0.78 (bleached state) and 0.24 (coloured state) at wavelength of 550 nm was deposited in an atmosphere of H₂(60%)+O₂(40%). Analysis of infrared spectra (60002400 cm⁻¹) showed that the absorption peaks for bleached and colored states are associated with free ‘OH’ and OH stretching vibrations, respectively. XPS Ni2p core level spectra of colored NiO_xH_y film exhibited a peak at 856.2±0.2 eV which is attributed to Ni³⁺. Ni2p core level spectra of the bleached and as-deposited films exhibited two peaks at 856.4±0.2 and 854.6±0.2 eV which are attributed to Ni³⁺ and Ni²⁺.     

Optimization of buffer layers for lattice-mismatched epitaxy of GaxIn1−xAs/InAsyP1−y double-heterostructures on InP

We optimize InAs_yP_1−y buffer layers and compositional grades for lattice-mismatched heteroepitaxy of Ga_xIn_1−xAs/InAs_yP_1−y double-heterostructures on InP. The strains of the active and buffer layers depend on the bulk misfit difference between these layers. The misfit difference is adjusted to eliminate strain in the active layer, thus avoiding misfit dislocations and surface topography that would otherwise form to relieve strain. The optimized structure uses an “overshoot” with respect to the conventional design in the misfit and As composition of the InAs_yP_1−y buffer. Nearly optimized heterostructures typically show excellent structural quality and extended minority-carrier lifetimes.     

Explosion behavior of CH4/O2/N2/CO2 and H2/O2/N2/CO2 mixtures

In this work, the explosion behavior of stoichiometric CH₄/O₂/N₂/CO₂ and H₂/O₂/N₂/CO₂ mixtures has been studied both experimentally and theoretically at different CO₂ contents and oxygen air enrichment factors. Peak pressure, maximum rate of pressure rise and laminar burning velocity were measured from pressure time records of explosions occurring in a closed cylindrical vessel. The laminar burning velocity was also computed through CHEMKIN–PREMIX simulations.     

Characterization and voltammetric behavior of PtyMozOx/C electrodes prepared by the thermal decomposition of polymeric precursors

Carbon-supported catalysts containing platinum and molybdenum oxide are prepared by thermal decomposition of polymeric precursors. The Pt_yMo_zO_x/C materials are characterized by energy dispersive X-ray spectroscopy, transmission electron microscopy, and X-ray diffraction. The catalysts present a well-controlled stoichiometry and nanometric particles. Molybdenum is present mainly as the MoO₃ orthorhombic structure, and no Pt alloys are detected. The voltammetric behavior of the electrodes is investigated; a correlation with literature results for PtMo/C catalysts prepared by other methods is established. The formation of soluble species and the aging effect are discussed.     

Structural and transport properties of LixNi1−y−zCoyMnzO2 cathode materials

In this work structural and transport properties of layered LiNi_1−y−zCo_yMn_zO₂ (y = 0.25, 0.35, 0.5 and z = 0.1) cathode materials are presented. In the considered group of oxides, LiNi_1−y−zCo_yMn_zO₂, there is no clear correlation between electrical conductivity and the a parameter (M-M distance in the octahedra layers). A non-monotonic modification of electrical properties of Li_xNi_0.65Co_0.25Mn_0.1O₂ cathode materials is observed upon lithium deintercalation.     

Experimental and modeling studies of C2H4/O2/Ar, C2H4/methylal/O2/Ar and C2H4/ethylal/O2/Ar rich flames and the effect of oxygenated additives

The addition of dimethoxymethane (DMM or methylal) and diethoxymethane (DEM or ethylal) to a rich ethylene/oxygen/argon flame has been investigated by measuring the depletion of soot precursors. Three rich premixed ethylene/oxygen/argon (with and without added methylal or ethylal) flat flames have been stabilized at low-pressure (50 mbar) on a Spalding–Botha type burner with the same equivalence ratio of 2.50. Identification and monitoring of signal intensity profiles of species within the flames have been carried out by using molecular beam mass spectrometry (M.B.M.S.). The replacement of some C₂H₄ by C₃H₈O₂ or C₅H₁₂O₂ is responsible for a decrease of the maximum mole fractions of the detected intermediate species. This phenomenon is noticeable for C₂–C₄ intermediates and becomes more effective for C₅–C₁₀ species, mainly when C₃H₈O₂ added.A new kinetic model has been elaborated and contains 546 reactions and 107 chemical species in order to simulate the three investigated flames: C₂H₄/O₂/Ar, C₂H₄/DMM/O₂/Ar and C₂H₄/DEM/O₂/Ar. The reaction mechanism well reproduces experimental mole fraction profiles of major and intermediate species, and underlines the effect of methylal and ethylal addition on species concentration profiles for these flames.     

Preparation and electrochemical properties of layer-structured LiNi1/3Co1/3Mn1/3−yAlyO2

Layer-structured LiNi_1/3Co_1/3Mn_1/3−yAl_yO₂ has been synthesized via a sol–gel method. The lattice constants of LiNi_1/3Co_1/3Mn_1/3−yAl_yO₂ decrease with the concentration of aluminum ions. XANES analysis further confirms that the valence of cobalt ion is 3+, and that of Ni is between 2+ and 3+ in LiNi_1/3Co_1/3Mn_1/3−yAl_yO₂. With doping aluminum ions, the redox centers for the electrochemical reaction change from nickel ions alone to both nickel and cobalt ions. The amounts of de-intercalatable lithium ions are affected by the concentration of aluminum ions; however, the extracting efficiency of lithium ions is improved by doping aluminum ions. Among all the samples, LiNi_1/3Co_1/3Mn_0.23Al_0.1O₂ exhibits the best capacity retention and the least irreversible capacity.