Study on the plasma treatment of waste oil containing PCB

The paper presents the results of treatment of transformer oil containing less than 2 ppm polychlorinated biphenyls (PCB) in a plant of high-temperature plasma melting of ash residues after the municipal waste incineration. The content of undecomposed PCBs, dioxins, and other hazardous waste in all secondary products of treatment (off gases; slag; secondary fly ash; process water used for slag granulation) was analyzed by different methods. Performed analytical investigations showed high ecological degree of PCB decomposition in the plant of plasma-thermal treatment of ashes after incinerators.     

垃圾焚烧灰渣的熔融物理化学特性分析

对垃圾焚烧灰渣的熔融物理化学特性研究,为合理应用和发展垃圾焚烧技术以及对灰渣的熔化处理和有效利用提供基础。本研究对目前运行的不同垃圾焚烧技术进行灰渣采样,系统分析垃圾灰渣的熔融物理化学特性的变化和相互关系,并给出灰渣流动温度和软化温度的拟合公式,并对垃圾焚烧技术及灰渣处理提出建议。     

预处理对垃圾焚烧飞灰玻璃化的影响

在垃圾焚烧飞灰进行熔融玻璃化之前,先用磷酸盐或绿矾溶液对飞灰进行洗涤,研究这种化学稳定化预处理对飞灰玻璃固化效果的影响。结果表明当使用磷酸盐溶液或磷酸盐与绿矾(FeSO4·7H2O)溶液一起对飞灰进行预处理、并且磷酸盐用量达2g磷/kg干灰时,对飞灰的熔融玻璃化有良好的促进效果,经过预处理后的飞灰通过玻璃化过程可实现对所检测的Pb、Hg、As、Cd、Cr五种重金属的全部稳定化,并且在熔融过程中烟尘的产生和重金属的挥发得到有效抑制。     

Mössbauer effect study of fly and bottom ashes from an electric generating plant

Samples of a fly ash and a bottom ash, each before and after ignition, have been investigated by X-ray diffraction and Mössbauer spectroscopy in order to explain the observed negative loss of ignition (LOI). It is shown that the ashes after ignition contain more maghemite resulting from newly formed magnetite. Moreover, the fly ash which contained already magnetite exhibited an increase of hematite after ignition. Both oxidation processes can be responsible for a weight gain which compensates the loss due to the burning of the remaining carbon. The magnetite and the alpha-iron formed after ignition is originated by an unidentified compound represented by a Fe^2?+? doublet in the Mössbauer spectrum.     

用XPS研究高灰熔融温度煤灰的矿物结构转化

高灰熔点X煤通过添加钙镁复配(W_CaO/W_MgO=1)助熔剂降低灰熔点,在模拟煤气化过程中制备灰渣,用X射线光电子能谱(XPS)分析不同温度点灰渣中O,Si,Al,Ca,Mg的存在形态及演化过程。认为钙镁复配助熔剂降低灰熔点主要是作用在硅、铝、氧结构变化上,表现为铝元素结构中铝氧配位方式的变化,即四配位的铝氧四面体[AlO₄]和六配位的铝氧八面体[AlO₆]随温度的变化而变化;硅元素结构中SiO₂链的破坏,Ca2+和Mg2+加入会破坏SiO₂链,使得桥氧硅变为非桥氧硅;以及氧元素结构中桥氧键断裂和非桥氧键形成。结合Factsage热力学分析软件,分析了添加钙镁复配助熔剂后,煤灰渣的高温相平衡组成,从矿物的结构变化研究助熔剂的助熔机理。结果表明,添加钙镁复配助熔剂后,Ca2+和Mg2+易与硅氧和铝氧四面体以及铝氧八面体中非桥氧键结合,生成低熔点的长石类矿物和镁质矿物,从而降低煤灰熔融温度。     

Mössbauer Studies of Thermal Power Plant Coal and Fly Ash

Iron-57 Mössbauer spectroscopic studies were carried out at room temperature on samples of coal, slag (bottom ash) and mechanical ash collected from Bhatinda (India) thermal power plant. Hyperfine parameters such as isomer shift, quadrupole splitting and total internal magnetic field of ⁵⁷Fe nuclei were used to characterize various iron-bearing minerals. The observed parameters indicate the presence of pyrite, siderite and ankerite in coal sample while magnetic fractions of mechanical ash and slag samples show the formation of hematite and Al-substituted magnesio-ferrite. The non-magnetic fraction of slag ash shows the dominance of Fe²⁺ phases while that of mechanical ash demonstrates the formation of both Fe²⁺ and Fe³⁺ phases. These findings are compared with Mössbauer and magnetic susceptibility studies on fly ash samples of Panipat (India) thermal power plant reported earlier.     

煤粉锅炉燃烧产物中汞,砷分布特征研究

对某300 MW燃煤电厂锅炉进行煤、渣、飞灰取样后,测定煤和燃烧产物中汞和砷的含量,研究了电除尘四个电场飞灰中汞与砷的分布特点。结果表明飞灰中砷的浓度随着粒度的降低而升高。在底渣中含量较低。通过飞灰粒度与砷浓度的拟合,初步得出砷的富集并不是只由物理凝结造成的,也有外部表面反应(或孔扩散)控制的过程。汞在电除尘1,2,3电场中是预料中的随着粒度的减小浓度增加。但在四电场中汞的浓度又降低了。通过分析得出飞灰含碳量也是影响汞吸附量的重要因素。     

Volt-ampere characteristics of a nitrogen DC plasma arc with anode melting

The characteristics of a nitrogen arc using a graphite cathode and a melting anode in a pilot-scale plasma furnace are investigated. The voltage is examined as a function of current and apparent plasma length. The voltage increases non-linearly with the increase of apparent plasma length, with the current fixed. The experimental data so obtained are compared with the predictions of the Bowman model for the electric arc, and with numerical simulations as well. The level of agreement between the experimental data at the melting anode and the numerical predictions confirms the suitability of the proposed the Bowman model. These characteristics are relevant to the engineering design and evaluation of a DC plasma furnace and reactor for the treatment of hazardous fly ash waste.     

煤粉低尘燃烧器热态试验研究

以液排渣旋风燃烧技术为基础的煤粉低尘燃烧器可在燃烧过程实现捕渣,为工业加热提供含尘浓度低的高温火焰,是工业加热过程实现以煤代油的先进燃烧技术。本论文介绍了新型煤粉低尘燃烧器的热态燃烧试验研究结果,该燃烧器采用端面旋流进风,煤粉和一次风在旋转气流外层送入,分级燃烧等技术。热态试验研究表明,采用上述技术的煤粉低尘燃烧器具有燃烧完全,捕渣率高,NOx排放浓度低等特点。     

Partitioning and transformation behavior of selenium during coal combustion

The partitioning of selenium in coal-fired flue gas and desulfurization wastewater is of great threat to the ecological environment and human health. However, the unclear understanding of interactions between selenium vapors and fly ash hinders the emission control of selenium from coal-fired power plants. To further illuminate the mechanism of selenium partitioning and transformation, this study carefully estimated selenium distribution characteristics in the coal combustion byproducts from several industrial power plants. The effective temperature range as well as the key ash components for selenium retention by fly ash was clarified by multiple-scale experiments and theoretical perspectives. The results showed that gaseous selenium tended to be captured by fly ash at a medium-to-low temperature range (i.e. below 650 °C). The limited residence time resulted in the incomplete capture of gaseous selenium by fly ash. Mullite, quartz, iron oxides, and anhydrite in fly ash were found to be the main trappers for gaseous selenium. Among these components, iron oxides showed excellent selenium adsorption performance at a wide temperature range of 150-700 °C, which was realized by the strong chemical adsorption. By contrast, as the dominant phases in fly ash for the physical adsorption of gaseous selenium, mullite and quartz mainly captured gaseous selenium below 300 °C. On the other hand, sulfur dioxides had priority over gaseous selenium to react with calcium-containing ash components by forming anhydrite in the high-temperature region. The formed anhydrite had a limited selenium adsorption capacity, which was confirmed to capture gaseous selenium through a combination of physical adsorption and weak chemical adsorption. For the in-depth control of selenium emitted into desulfurization system and atmosphere environment, these findings provided a comprehensive insight into the behavior of selenium partitioning and transformation into fly ash during coal combustion.     

矿物掺合料作为砂浆细集料的水化产物与光谱性能研究

粉煤灰、锂渣和钢渣作为工业废渣,等质量替代水泥时其利用率往往较低,为了大量地使用这些工业废渣。采用X射线单晶衍射仪、同步热分析仪、傅里叶红外光谱仪和电镜扫描分析方法,研究了锂渣、粉煤灰和钢渣替代细集料后砂浆的水化产物、光谱特性、微观形貌,并探讨了砂浆抗折/抗压强度随替代率(0%,30%,50%,70%和100%)增长的变化规律。研究结果表明：四种浆体的水化产物主要为CSH凝胶、Ca(OH)₂、少量的AFt和未水化的颗粒(Al₂O₃,SiO₂),其中水泥-锂渣浆体、水泥-粉煤灰浆体、水泥-钢渣浆体中的未水化颗粒还含有一定的Li₂O·Al₂O₃·SiO₂,Ca_1.56SiO_3.5·xH₂O和RO phas。四种浆体以3 467,3 438,2 923,2 348,1 638,1 429,1 111,1 000,768,696和462 cm-1为特征峰,但其峰强有所不同,其活性也不同,参与二次水化反应的程度也不同,因此,水泥-钢渣浆体中Ca(OH)₂的含量明显高于水泥-粉煤灰浆体和水泥-锂渣浆体的现象;但不管是矿物掺合料替代水泥还是细集料,都在浆体中发挥着火山灰活性和填充作用。含三种100%矿物掺合料砂浆的抗折强度和抗压强度均高于纯水泥砂浆,分别(锂渣、粉煤灰和钢渣)约高37.77%/51.88%,14.71%/11.70%,91.95%/34.88%,但其达到峰值的掺量不同。因此,采用矿物掺合料替代细集料是可行的,能大幅度提高工业废渣在混凝土行业中的使用,且能达到节能减排的效果。     

粉煤灰地聚合物固封Cr3+的FTIR和XPS研究

采用傅里叶变换红外光谱(FTIR)和X射线光电子能谱分析(XPS)研究了粉煤灰地聚合物固封Cr3 的机理。含Cr的污泥由人工合成,主要成分是Cr(OH)3。浸出试验采用ICP-AES方法,测试了固封Cr3 前后,粉煤灰地聚合物中Al和Si的浸出量;研究结果表明,掺入含Cr的污泥后,粉煤灰地聚合物中Si和Al元素的浸出量较不掺污泥时减少了,且浸出Si元素减少的幅度比浸出Al元素降低的幅度要大。FTIR结果显示,Cr3 的掺入削弱了粉煤灰地聚合物主峰的强度,增加了Si—O—Si和Al—O—Si的振动波数;XPS测试结果表明,O(1s),Si(2p)和Cr(2p)的结合能都有不同程度的改变,而Al(2p)的结合能几乎没有发生变化;结果揭示Cr3 参与了粉煤灰地聚合物中硅酸结构的聚合,粉煤灰地聚合物固封Cr3 ,不仅仅只是物理性的包裹作用,而且主要是化学反应的结果。     

激光能量对飞灰颗粒流中未燃碳LIBS检测影响研究

飞灰含碳量是评价锅炉燃烧效率的重要指标之一,对其进行在线测量有助于实时进行燃烧优化调整,从而提高整个机组的经济性和安全性。利用螺杆式给粉机搭建飞灰颗粒流含碳量测量台架,将脉冲激光直接作用于飞灰颗粒流,形成等离子体,利用激光诱导击穿光谱技术测量飞灰颗粒流中的含碳量信息。重点研究了激光能量对飞灰颗粒流中未燃碳有效激发和测量的影响规律。研究结果显示,在40～130 mJ能量的脉冲激光作用下,碳谱线强度随着激光能量的增大线性增强,而其信噪比则先增加后趋于稳定,无效光谱的剔除率则呈下降趋势。本实验条件下,激光能量在90～100 mJ之间,可得到较强的等离子体发射信号和较优的光谱数据利用率。因而激光能量与颗粒流的激发状态、碳元素特征谱线强度等密切相关。合理的激光能量有利于保证飞灰颗粒流的有效稳定激发,并获得具有良好信噪比的等离子体光谱信号。     

激光能量对粉煤灰未燃碳测量的影响

搭建了基于激光诱导击穿光谱技术的成分分析应用研究台架,应用于粉煤灰未燃碳的检测,考察不同能量的脉冲激光烧蚀粉煤灰样品时的等离子体特性。使用多通道光纤光谱仪和CCD探测器对激光烧蚀形成的等离子体发射信号进行分光和探测。分析碳谱线强度、等离子体温度和电子密度随激光能量变化的趋势,掌握激光能量对粉煤灰未燃碳测量的影响规律。研究结果显示,随着激光能量的增大,碳谱线强度、等离子体温度和电子密度均先增大后减小,空气击穿明显增强。随后碳谱线强度的变化趋于平缓并开始下降。合适的激光能量可以增强等离子体发射信号,并避免强烈空气击穿的不利影响,有助于提高测量精度。     

煤粉旋风燃烧过程流场特性研究

煤粉旋风燃烧器可用于工业加热过程,实现以煤代油,本论文根据旋流燃烧流动特点,采用能考虑非均向湍流应力的雷诺应力模型,对煤粉旋风燃烧器内气流流动过程场进行数值模拟计算,流场计算结果表明,燃烧室几何参数对其内部的流动特性有很大的影响。计算结果与流场实验测试相吻合。     

Trace element analysis of fly ash samples by EDXRF technique

Trace element analysis of some fly ash samples and soil samples have been carried out by Energy Dispersive X-Ray Fluorescence technique. Fourteen elements namely K, Ca, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Se, Rb, Sr and Pb have been quantified in the fly ash samples by this technique. It was found that there is no huge concentration difference between the fly ash and soil samples as a result of which fly ash can be used as soil manure without any adverse impact on the plants.      

ICP-OES分析低钙粉煤灰在NaOH溶液中离子浸出规律

低钙粉煤灰潜在的火山灰活性释放缓慢限制了其大规模利用,通过碱激发提高粉煤灰中Si4+,Al3+和Ca2+等离子浸出率对于加快低钙粉煤灰活性释放具有积极作用。采用电感耦合等离子体发射光谱、傅里叶变换红外光谱、X射线衍射和扫描电子显微镜分别测试和分析了5种浓度NaOH溶液对低钙粉煤灰激发过程中Si4+,Al3+和Ca2+的浸出规律、化学基团变化、水化产物生成及微观形貌演化。结果表明：碱激发作用显著提高了低钙粉煤灰中Si4+,Al3+和Ca2+浸出率,三种离子浸出率大小为：Si4+＞Al3+＞Ca2+,其中Si4+和Al3+浸出率随NaOH浓度增加而增加,随浸出时间延长呈对数规律升高;Ca2+由于在NaOH溶液中生成Ca(OH)₂沉淀,其浸出率大小表现为在水中高,在NaOH溶液中低。红外光谱清晰地表征出低钙粉煤灰受碱激发作用后化学基团在指纹区(波数1 300 cm-1以下)的变化,且随碱激发时间的延长和碱浓度的增加变化愈加明显。水化产物和微观形貌的结果显示出粉煤灰颗粒表面受到碱侵蚀发生解聚,在OH-催化下,硅铝单体分子重新排列形成硅酸盐和铝酸盐低聚络合物,通过亲核取代反应形成铝硅酸盐的低聚态溶胶,并进一步与碱金属阳离子通过配位键或静电键的作用缩聚形成水化凝胶类产物。采用ICP-OES测试粉煤灰中离子浸出率可作为评价粉煤灰火山灰活性的一种快速和准确的方法。     

Optical emission spectroscopy of point-plane corona and back-corona discharges in air

Results of spectroscopic investigations and current-voltage characteristics of corona discharge and back discharge on fly-ash layer, generated in point-plane electrode geometry in air at atmospheric pressure are presented in the paper. The characteristics of both discharges are similar but differ in the current and voltage ranges of all the discharge forms distinguished during the experiments. Three forms of back discharge, for positive and negative polarity, were investigated: glow, streamer and low-current back-arc. In order to characterize ionisation and excitation processes in back discharge, the emission spectra were measured and compared with those obtained for normal corona discharge generated in the same electrode configuration but with fly ash layer removed. The emission spectra were measured in two discharge zones: near the tip of needle electrode and near the plate. Visual forms of the discharge were recorded with digital camera and referred to current-voltage characteristics and emission spectra. The measurements have shown that spectral lines emitted by back discharge depend on the form of discharge and the discharge current. From the comparison of the spectral lines of back and normal discharges an effect of fly ash layer on the discharge morphology can be determined. The recorded emission spectra formed by ionised gas and plasma near the needle electrode and fly ash layer are different. It should be noted that in back arc emission, spectral lines of fly ash layer components can be distinguished. On the other hand, in needle zone, the emission of high intensity N₂ second positive system and NO _γ lines can be noticed. Regardless of these gaseous lines, also atomic lines of dust layer were present in the spectrum. The differences in spectra of back discharge for positive and negative polarities of the needle electrode have been explained by considering the kind of ions generated in the crater in fly ash layer. The aim of these studies is to better understand the discharge processes encountered in electrostatic precipitators.     

利用红外光谱确定碱法分解粉煤灰的碳酸钠用量的实验研究

利用红外光谱研究了粉煤灰在用碳酸钠碱熔法分解前后的物相变化,发现： 碱熔前,粉煤灰的红外光谱主要显示莫来石和二氧化硅的特征吸收;碱熔后,粉煤灰(后统称熟料)的红外光谱主要表现为霞石的特征吸收。研究还对比了不同配比条件下,莫来石反应的完全程度。发现不同配比的粉煤灰熟料的红外光谱存在很大差异。在一定的碳酸钠用量范围内(粉煤灰∶碳酸钠＞1.2∶1时),其对应熟料的红外光谱主要为霞石的吸收峰,并表现有莫来石吸收残留,说明此配比条件下,莫来石尚未分解完全;当粉煤灰∶碳酸钠＝1.2∶1时,莫来石吸收消失,说明此配比条件下,莫来石可以分解完全,此时熟料的红外光谱中也未出现其他杂峰,证明此时熟料为霞石单一物相;当粉煤灰∶碳酸钠＜1.2∶1时,熟料的红外光谱中出现了碳酸盐的特征吸收,说明碳酸钠过量,同时,硅酸根的特征吸收峰也发生分裂,说明硅酸根的振动吸收峰增加,推测可能是碳酸钠过量后,霞石与碳酸钠发生反应,使霞石吸收过量的Na₂O,导致霞石的晶体结构发生变化。由此可以判定碱熔法分解粉煤灰的最佳配比为粉煤灰∶碳酸钠＝1.2∶1。X射线分析也得到了相同的结论。     

Synchrotron‐radiation‐induced oxidation of selenite to selenate in coal‐derived fly ash

Systematic changes observed in consecutive XANES spectra of selenium in samples of fly ash from a power plant in Alberta, Canada, burning subbituminous coal have been interpreted as arising from synchrotron‐radiation‐induced oxidation of a selenite species to selenate. It was estimated that about 15–20% of the selenite was oxidized to selenate during the 2 h exposure of the fly ash to the synchrotron beam. In contrast, the XANES spectra of arsenic (and other trace elements not documented herein) showed no variation. It is believed that this is the first time that radiation‐induced changes have been observed for an element in coal‐derived fly ash.