Development of novel refractory ceramic continuous fibers of fly ash and comparison of mechanical properties with those of E-glass fibers using the Weibull distribution

This study aimed to develop manufacturing technology for high-strength refractory ceramic fibers (RCFs) using fly ash, which is a highly promising material for the exterior and thermal insulation industry. The technology also contributes to reducing the environmental pollution caused by landfilling fly ash after coal is burned. Fly ash discharged from a thermal power plant, which had aluminosilicate chemical compositions, was used as the main material. As auxiliary materials, basalt, anorthite, feldspar, dolomite, and calcite were used to adjust the melt flowability, and frit, silica sand, and burr stone were used to lower the melting temperature. Moreover, the development of aluminosilicate fly ash fiber has the advantages of lower cost for raw materials and processing. Fly ash and natural rocks are inexpensive, and most of all, unlike the case for glass fiber production, the high cost of B₂O₃ is not a necessary expense. Fly ash is retrieved in powder form, which is advantageous compared to the starting materials for glass; the grinding process of raw materials can be skipped. From the fibrilization index calculation, we showed that the spinnability was influenced by the chemical composition of the salt-forming oxides in the fly ash compounds. We also found a correlation between the winding speed and the fiber diameter. The mechanical properties of a series of fly ash fibers were assessed by the Weibull distribution and then compared with those of the E-glass fibers that were melt-spun under an analogous condition.     

Crystallisation behaviour of blast furnace slag modified by adding fly ash

Crystallisation of molten blast furnace (BF) slag can increase its viscosity, which can in turn affect the quality of slag fibres. Fly ash was added to BF slag to control its crystallisation and modify its chemical composition. FactSage simulation and analyses using X-ray diffraction (XRD), scanning electron microscope-backscattered electrons (SEM-BSE) coupled to an energy dispersive spectrometer (EDS), and single hot thermocouple technique (SHTT) were performed to explore the crystallisation behaviour of the modified BF slag. The relationship between temperature, mineral precipitation, and added fly ash content was investigated. The minerals contained in the modified BF were melilite, anorthite, clinopyroxene, and spinel. Variation in the fly ash content did not change the composition of the precipitate, but changed its content and the crystallisation temperature of the minerals, which affects the initial crystallisation temperature of the modified BF slag. It decreased as fly ash content increased, and was influenced by the crystallisation of melilite when the added fly ash content was between 5% and 20%. When the added fly ash content increased to 25%, the initial crystallisation temperature was influenced by the precipitation of anorthite. The initial crystallisation temperatures obtained by FactSage simulation, XRD analysis, and SHTT experiments differed due to kinetic effects. The modified BF slag with a fly ash content of 15% is considered suitable for manufacturing of slag fibres due to its low initial crystallisation temperature and cost.     

Nucleation and Crystallization of New Glasses from Fly Ash Originating from Thermal Power Plants

The nucleation and crystallization kinetics of new glasses obtained by melting mixtures of a Spanish carbon fly ash with glass cullet and dolomite slag at 1500°C has been evaluated by a calculation method. These glasses, whose microstructure was examined by TEM carbon replica, were susceptible to controlled crystallization in the 800°–1100°C range. The resulting glass-ceramics developed acicular and branched wollastonite crystals or a network of dendritic pyroxene mixed with anorthite feldspar (SEM and EDX analysis). The time–temperature–transformation curves (processing of the XRD data) showed the crystallization kinetics and the critical cooling rate to be in the 12°–42°C/min range.     

Effect of CaO/SiO2 ratio on phase transformation and properties of anorthite-based ceramics from coal fly ash and steel slag

Anorthite-based ceramics were produced entirely from coal fly ash and steel slag. The effect of the CaO/SiO₂ ratio (0.12–0.8) on the phase transitions was examined by adding steel slag to coal fly ash in the range of 10–50 wt%, and a temperature range of 900–1200 °C. The influence of CaO/SiO₂ and sintering temperatures on the technological properties were assessed by response surface methodology (RSM) and correlated with the phase changes. The results revealed that anorthite was the main phase for the CaO/SiO₂ ratio ranging from 0.12 to 0.56, while at 1200 °C, a ratio of 0.8 involved a high content of gehlenite. RSM showed that the CaO/SiO₂ ratio was the main influencing factor on the density, while the variation of apparent porosity and compressive strength were more affected by sintering temperature. The crystallisation of the anorthite phase significantly enhanced the properties of the obtained ceramics, whereas the appearance of gehlenite reduced the mechanical strength. The optimum conditions to fabricate anorthite-based ceramics with suitable properties were found to be a CaO/SiO₂ ratio of 0.46 and a temperature of 1188 °C. The optimised anorthite-based ceramic exhibited a low thermal conductivity (0.39 W/m.K) and a dielectric constant of 6.03 at 1 MHz, along with a compressive strength of 41 MPa, which makes this sample a potential candidate for insulator applications.     

残炭对高镁煤灰熔融特性影响机制研究

为研究残炭对高镁煤灰熔融特性的影响,选取典型宁东气化用煤——梅花井煤为原料进行了不同残炭质量分数煤灰的灰熔融温度(t_AF)测试。利用FactSage7.3热力学软件对煤灰熔融过程进行模拟计算,探究了不同残炭质量分数煤灰在一定温度区间内的矿物转变。利用X射线衍射(XRD)和扫描电子显微镜结合能量色散光谱仪(SEM-EDS)分别对煤灰的矿物质组成及微观形貌进行了表征。结果表明:在煤灰熔融过程中,钙长石和辉石类矿物质在1275℃开始熔融为液相,其含量明显降低,煤灰的熔融是熔融-溶解机制;煤灰在熔融过程形成大量的低温共熔物(橄榄石、尖晶石和辉石)主导了煤灰的熔融温度,从而使得煤灰的熔融温度较低;随着残炭质量分数增加,低熔点矿物尖晶石含量急剧增加,煤灰的熔融温度呈降低趋势,这是由于氧化镁的离子势较低(3.0);在高温条件下MgO对煤灰中其他组分的作用是氧给予体,而残炭的存在能够剥夺氧化镁中的氧,从而阻止多聚物聚集,引起煤灰熔融温度降低。     

Effect of Al2O3/CaO on the melting and mineral transformation of Ningdong coal ash

Coal ash melting characteristics has a direct impact on the smooth operation of entrained gasifier. Mineral conversion of coal ash is very significant to be investigated, because the mineral can affect the melting temperature and viscosity under high temperature conditions. In this paper, the effects of different Al₂O₃/CaO on the mineral conversion, melting temperature and viscosity of Ningdong coal ash are studied by the combination of experiment and simulation. The trend of melting temperature decreases firstly and rises with increasing Al₂O₃/CaO. The ash melting point reached to the lowest when the ratio is 1.23. XRD and Factsage software are used to analyze crystallization behavior of samples. The results show that the content of anorthite, albite and corundum increases and subsequently decreases, while the content of mullite decreases firstly and then rises with increasing Al₂O₃/CaO. High content with CaO can contribute to form albite and anorthite of low-melting. Besides, high content with Al₂O₃ can tend to produce mullite of high-melting. The results of experimental and simulation are basically the same, which lays a foundation for the melting characteristics of Ningdong coal ash and can provide technical support for the smooth operation of the entrained-gasifier.     

硅锰渣复合粉煤灰水热合成NaA沸石及其表征

对硅锰渣进行高温煅烧预处理,并复合粉煤灰作为原料,采用水热法合成了结晶度良好的NaA沸石。研究了硅铝比(n(SiO₂)/n(Al₂O₃))、碱度(c(NaOH))、水热温度以及水热时间等条件对合成产物的影响。结果表明:在煅烧硅锰渣与粉煤灰以质量比为1∶1,n(SiO₂)/n(Al₂O₃)=2.2,反应温度为90 ℃,碱度为2 mol/L,反应时间为4 h的条件下即可合成结晶度良好且具备一定热稳定性的NaA沸石。相较于传统的以粉煤灰为原料合成NaA沸石,本实验掺入硅锰渣形成复合体系,为硅锰渣的资源化利用提供了新途径。     

原料组成对粉煤灰熔融温度的影响研究

以粉煤灰为主要原料,硼砂、钾长石和白云石为助熔剂,运用SJY影像式烧结点试验仪观察试样在高温情况下,其体积收缩、膨胀钝化及完全球化等变化情况,并记录各种情况发生时的相应温度,研究不同种类助熔剂及其加入量与熔融温度的关系,确定粉煤灰泡沫陶瓷制备的基础配方.实验结果表明:当原料组成为粉煤灰50wt%,硼砂为10wt%,钾长石和白云石总加入量为40wt%且钾长石∶白云石=3∶1时,试样的各项性能指标较佳.     

Operation performance of a pilot-scale gasification/melting process for liquid and slurry-type wastes

A gasification/melting facility that can operate up to 10 bar and 1,550 °C with a maximum 1 ton/day capacity was developed for liquid and slurry-type combustible wastes. The main focus of the system development was minimal use of expensive fuel for maintaining the reaction temperature by replacing it with cheap waste oil for energy input. The carbon conversion obtained was 97% while the cold gas efficiency reached 77.6% for the refined waste oil. When the feed was refined oil mixed with fly ash from a municipal waste incinerator, the carbon conversion and cold gas efficiency were 93% and 71.9%, respectively, with a slag conversion ratio of 0.93. The slag produced from fly ash exhibited environmentally acceptable heavy-metal leaching values and thus can be applicable as road material and for other purposes. The optimal O₂/feed ratio was 0.9–1.0 when only the refined waste oil was gasified, whereas the O₂/feed ratio had to be higher than 1.2 when fly ash was mixed. In addition, data showed that gasifier temperature can be estimated by on-line methane concentration measurements.     

Flux mechanism of compound flux on ash and slag of coal with high ash melting temperature

The melting temperature of Z coal ash was reduced by adding calcium–magnesium compound flux(W_(CaO)/W_(MgO)=1). In the process of simulated coal gasification, the coal ash and slag were prepared. The transformation of minerals in coal ash and slag upon the change of temperature was studied by using X-ray diffraction(XRD). With the increase of temperatures, forsterite in the ash disappears, while the diffraction peak strength of magnesium spinel increases,and the content of the calcium feldspar increases, then the content of the amorphous phase in the ash increases obviously. The species and evolution process of oxygen, silicon, aluminum, calcium, magnesium at different temperatures were analyzed by X-ray photoelectron spectroscopy(XPS). The decrease of the ash melting point mainly affects the structural changes of silicon, aluminum and oxygen. The coordination of aluminum and oxygen in the aluminum element structure, e.g., tetracoordinated aluminum oxide, was changed. Tetrahedral [AlO_4] and hexacoordinated aluminoxy octahedral [AlO_6] change with the temperature changing. The addition of Ca~(2+) and Mg~(2+) destroys silica chain, making bridge oxide silicon change into non-bridge oxysilicon; and bridge oxygen bond was broken and non-bridge oxygen bond was produced in the oxygen element structure. The addition of calcium and magnesium compound flux reacts with aluminum oxide tetrahedron, aluminum oxide octahedron and silicon tetrahedron to promote the breakage of the bridge oxygen bond. Ca~(2+) and Mg~(2+) are easily combined with silicon oxide and aluminum oxide tetrahedron and aluminum. Oxygen octahedrons combine with non-oxygen bonds to generate low-melting temperature feldspars and magnesite minerals, thereby reducing the coal ash melting temperatures. The structure of kaolinite and mullite was simulated by quantum chemistry calculation, and kaolinite molecule has a stable structure.     

Preparation of low melting temperature glass-ceramics from municipal waste incineration fly ash

Glass-ceramics have been prepared from air pollution control residues (fly ash) of a municipal solid waste incineration (MSWI) plant in southern China. The use of additives was investigated in order to decrease the melting temperature of the waste and thus to reduce the costs of production of glass-ceramics from the vitrified waste. Results showed that the melting temperature can be decreased significantly from 1500 to 1200 °C, which was achieved by combining the MSWI fly ash with silica sand powder and a Fe₂O₃-rich and CaO-rich iron slag to form a glass in the SiO₂-CaO-Al₂O₃-Fe₂O₃ quaternary phase system. Sodium carbonate and borax were used as fluxing agents and TiO₂ of chemical grade was added as a nucleation agent. The main crystalline phase in both high and low melting temperature glass-ceramics was found to be diopside (Fe-bearing), and the microstructure exhibited the presence of fine crystals of size in the range 100-200 nm which developed at crystallization temperatures in the range 800-900 °C for 1-2 h. The leaching behaviour of the glass-ceramic materials was tested, and it was found to be lower than that of a cement-stabilized body that was fabricated using the same waste for comparison. The results demonstrate the feasibility of reusing MSWI fly ash for glass-ceramic production at relatively low melting temperature, e.g. in a less energy-intensive process, as a viable approach for tackling the problem of hazardous MSWI residues.     

镁渣粉煤灰复掺配制混凝土的自收缩特性

为了探索镁渣与粉煤灰复掺对混凝土自生收缩的作用规律,设计正交试验方案研究了混凝土的自生收缩特性,微观分析掺合料的形貌与作用机理.结果表明:镁渣和粉煤灰对混凝土的自生收缩具有显著的抑制效应,镁渣与粉煤灰的掺量由(10%,15%)增加到(40%,30%),混凝土180 d的自生收缩变形减少约44.0%;混凝土自生收缩在镁渣掺量为30%~40%区间上的极差较镁渣掺量为10%~20%区间上的极差增大3.5倍,混凝土自生收缩变形的敏感性在镁渣掺量高时相对较大;混凝土的自生收缩变形主要发生在早期,28 d就完成了测定龄期内总自生收缩变形的65.0%~80.0%,早期是混凝土收缩变形控制的重要阶段;自生收缩的模型预测值与实测值间的偏差小,可用于复掺镁渣粉煤灰混凝土自生收缩的分析与预测.     

The effect of increasing MgO content in dendromass on ash fusibility and corrosion of corundum refractory castable

Low melting temperatures of the biomass ash at the intensive combustion can generate the slag with a portion of unburned fuel. The portion of imperfectly burned fuel reduces the efficiency of its use. An alternative route to solve the problem without changing the combustion condition is a modification of the chemical composition of the ash with the addition of an agent increasing the melting temperature of the ash/slag. In this paper, we report on the impact of adding the magnesite waste sludge to ash on their melting. Three types of ashes with different SiO₂ and K₂O content were selected for the tests. The melting temperatures of ash and ash mixtures with magnesite sludge (mass ratio 0.5–2:1) have been determined. The addition of magnesite sludge to ash increased the temperature of fusibility index of the mixtures by 50–100 °C. The ash fusibility temperature rose with a decrease of the SiO₂ content in the ash. Subsequently, the interaction of the ash/ash mixtures with the refractory corundum castable was monitored at a temperature of 1450 °C using a static crucible corrosion test. The addition of magnesite sludge to ash reduced the aggression of the slags to the refractory corundum materials. The Al₂O₃ concentration in the post mortem slags of the ash mixtures with the magnesite sludge (2:1) was about 20–23 wt% lower in comparison to the slag without magnesite. The evaluation of the effect of magnesite sludge addition to ash and the elements (K, Ca, Mg, Fe, Si) penetration on the extent of corrosion is the subject of further work aimed at analyses of the corrosion interface of the slag – corundum refractory material.     

Behaviour of calcium-containing minerals in the mechanism towards in situ CO2 capture during gasification

Mineral matter transformation and the behavior of mineral matter in the coal during gasification, provide more information on the suitability of a specific coal source for combustion or gasification purposes. Therefore, the chemistry and mineral interactions have to be understood in order to determine the suitability for fixed bed gasification purposes with regards to mineral matter transformations and slagging properties.Although a suite of minerals important for the gasification process were identified [Van Dyk JC, Melzer S, Sobiecki A. Mineral matter transformations during Sasol-Lurgi fixed bed dry bottom gasification - utilization of HT-XRD and FactSage modelling. Minerals Engineering 2006; 19: 1126-35], some of the minerals, i.e. anorthite and calcite, with a specific behavior at different concentrations in the mineral structure and the transformation thereof was not studied and highlighted in detail. A number of other researchers [Reifenstein AP, Kahraman H, Coin CDA, Calos NJ, Miller G, Uwins P. Behavior of selected minerals in an improved ash fusion test: quartz, potassium feldspar, sodium feldspar, kaolinite, illite, calcite, dolomite, siderite, pyrite and apatite. Fuel 1999; 78: 1449-61], [Kondratiev A, Jaks E. Predicting coal ash slag flow characteristics (viscosity model for the Al₂O₃-CaO-‘FeO’-SiO₂ system). Fuel 2001; 80: 1989-2000] and [Kondratiev A, Jak E. Applications of the coal ash slag viscosity model for the slagging gasification technologies (viscosity model in the Al₂O₃-CaO-‘FeO’-SiO₂ system), 18th Pittsburgh Coal Conference, Newcastle, Australia, December 2001]) also did not investigate these gasification changes and mineralogical deformation during specific gasification conditions in detail.The principle aim of this paper is to identify the role of Ca-containing mineral species towards the in situ capture of CO₂ during gasification, as well as understanding the chemistry and interpret the mechanism of CO₂ capture by means of high temperature X-ray diffraction (HT-XRD), in combination with FactSage modeling. The CaO content of a South African and another coal source investigated in the present study, were 6 mass% and 30 mass% respectively. The basic components present in the coal, or specifically CaO, only act as a fluxing component up to a specific percentage, where after the ash fusion temperature starts to increase again. At this turning point the (Si+Al):Ca molar mass ratio is 2.75, which implies that after the turning point, the formation of anorthite is maximized and can thereafter only remain at the same level.The anorthite formation, when the Ca content increases, follows the inverse trend of the ash flow temperature prediction curve with the coal containing 6% CaO. The decrease in anorthite formation, with increasing Ca content, after the turning point in the graph, can be explained by the fact that more of the crystalline phase becomes a liquid (slag), and thus also the increase in the amount CaO in the slag will be observed. At the turning point, it is also interesting to note the stabilisation of the amount of other Ca-containing species. These are the minerals that are responsible and available for the mechanism where CO₂ can be captured on Ca to form CaCO₃. The formation of CaCO₃ can also be observed from the turning point where the (Si+Al):Ca molar mass ratio is <2.75, which corresponds with the formation of other Ca-containing species.Thermodynamic modeling with FactSage results indicated that anorthite can only form to the point where the (Si+Al):Ca molar mass ratio is >2.75. Anorthite (CaSi₂Al₂O₈) forms within the gasification zone and all non-reacted Ca react with CO₂ to form CaCO₃ further down in the combustion zone.     

硅铝比对钙镁耦合作用降低煤灰熔融性的影响研究

利用化学试剂配制不同硅铝比的模拟煤灰,探究不同硅铝比模拟灰的流动温度随灰中钙镁配比的变化规律;并借助XRD、SEM-EDX分析矿物转化过程,初探钙镁耦合作用发生机理.结果表明:随着硅铝比的增加,钙镁耦合作用降低煤灰熔融性的强度先增大后减弱,且在Si/Al为1.5时最大;钙长石与镁橄榄石发生低温共熔是钙镁耦合作用降低煤灰熔融性的主要原因.Si/Al为1.0和4.0时,随着模拟灰中镁钙比的增大,钙长石低温共熔体系及辉石类矿物低温共熔体系的建立,使得煤灰流动温度一直下降,未表现出耦合作用.钙镁含量相同的灰渣中,随硅铝比的增加,灰渣由片块状向团聚状、絮状转变;SEM-EDX分析结果与XRD分析结果一致.     

Enriched‐Air Gasification of Refuse‐Derived Fuel in a Fluidized Bed: Effect of Gasifying Conditions and Bed Materials

Enriched‐air gasification of refuse‐derived fuel (RDF) was carried out in a fluidized bed, investigating the effects of temperature, equivalence ratio (ER), oxygen percentage of enriched air (OP), and bed materials. For the bed material effect, calcined dolomite proved to be more effective for tar decomposition and resulted in higher CO and H₂ contents. In a bed of high‐alumina bauxite, an increased ER tended to cause a greater decrease in syngas quality. For both bed materials, a higher temperature and OP favored the production of combustible gas and led to higher cold gas efficiency. Increasing the ER resulted in higher gas yields and carbon conversion but lowered the concentration of the combustible component. The ash content of the char increased with temperature and OP, while the volatile and fixed carbon contents were decreased. The optimum conditions suggested in this study were an ER of 0.22 and an OP of 44.7 % at 750–800 °C in a bed of calcined dolomite.     

Thin fly ash/ ladle furnace slag geopolymer: Effect of elevated temperature exposure on flexural properties and morphological characteristics

The flexural properties and thermal performance of 10 mm-thin geopolymers made from fly ash and ladle furnace slag were evaluated before and after exposure to elevated temperatures (300 °C, 600 °C, 900 °C, 1100 °C and 1150 °C). Class F fly ash was mixed with liquid sodium silicate (Na₂SiO₃) and 12 M sodium hydroxide (NaOH) solution using aluminosilicate/activator ratio of 1:2.5 and Na₂SiO₃/NaOH ratio of 1:4 to synthesise thin fly ash (FA) geopolymers. 40 wt% of ladle furnace slag was partially replacing fly ash to produce fly ash/slag-based (FAS) geopolymers. Thermal treatment enhanced the flexural strength of thin geopolymers. In comparison to the unexposed specimen, the flexural strength of FA geopolymers at 1150 °C and FAS geopolymers 1100 °C was increased by 161.3% to 16.2 MPa and 208.9% to 24.1 MPa, respectively. A more uniform heating was achieved in thin geopolymers which favoured the phase transformation at high temperatures and contributed to the substantial increase in flexural strength. The joint effect of elevated temperature exposure and the incorporation of ladle furnace slag further improved the flexural strength of thin geopolymers. The calcium-rich slag refined the pore structure and increased the crystallinity of thin geopolymers which aided in high strength development.     

复掺混合材对水泥及混凝土性能影响的试验研究

研究了石灰石、矿渣、烧页岩及粉煤灰四种混合材复配对水泥及混凝土性能的影响。试验结果表明,矿渣和石灰石有益于改善水泥的标准稠度用水量、外加剂相容性、混凝土的工作性能及强度,而烧页岩和粉煤灰有益于水泥的强度,几种混合材的合理搭配可以改善水泥和混凝土的性能。     

铁钙比对煤灰中耐熔矿物生成的抑制机理研究

铁基助熔剂和钙基助熔剂能有效降低煤灰熔融温度,为了研究铁钙比(Fe2O3/CaO)对煤灰中耐熔矿物生成的抑制机理,根据煤灰化学成分组成,在三种不同系列的煤中加入含铁助剂,调整煤中的铁钙比,对煤灰进行灰熔融温度、煤灰成分分析,对还原性气氛下制备的煤灰渣进行X射线衍射分析(XRD).结果表明:加入含铁助剂可降低煤灰熔融温度,在相同铁钙比下,加入Fe助剂的煤灰熔融温度低于加入FeS2助剂的煤灰熔融温度,硫在煤灰中起增加煤灰熔融温度的作用;煤灰中铁钙比不同对高熔点矿物的生成影响不同,当铁钙比在1~2间时,灰渣中仅有钙长石,当铁钙比在3.5~5.5间时,灰渣中既有钙长石的也有耐熔矿物莫来石的存在,煤灰中铁质矿物和钙质矿物的含量对耐熔矿物的生成有很大影响.     

水淬渣-粉煤灰基4A沸石的制备及性能表征

粉煤灰因其主要成分为二氧化硅、三氧化二铝常被用来当作合成沸石的原材料,合成的沸石类型主要有X型、Y型、A型、ZSM-5型等,相关合成技术也已非常成熟。水淬渣是高炉炼铁水淬急冷产生的高炉渣,对其主要利用方式是作为水泥、路基材料,均属低附加值利用。通过碱熔水热法利用水淬渣、粉煤灰混合原料合成4A型沸石。初步探究硅铝物质的量比（简称硅铝比）、熔融温度、熔融时间、晶化时间对制备的沸石样品品质造成的影响,得到最佳制备条件：硅铝比为1.0、碱灰质量比为1.5、碱熔时间为1 h、碱熔温度为600 ℃、老化时间为12 h、灰水质量比为1∶5、晶化温度为90 ℃、晶化时间为16 h。对合成的沸石进行X射线衍射（XRD）、X射线荧光光谱（XRF）、扫描电镜（SEM）、红外光谱（FT-IR）等表征,结果表明利用水淬渣、粉煤灰合成的4A型沸石各方面性能良好,具有超高的工业化生产价值。