城市生活垃圾焚烧飞灰组成特性及重金属熔融固化处理技术研究进展

近年来,我国城市生活垃圾清运量以每年5%左右的增速发展,垃圾焚烧处理能力不断提升,而垃圾焚烧过程会产生占焚烧总量3%~5%的垃圾焚烧飞灰。随着垃圾焚烧处理能力的不断提升,垃圾飞灰产量逐年增加,飞灰处置压力越来越大。城市生活垃圾焚烧飞灰作为一种高重金属浸出毒性的危险废弃物,对环境存在较大危害。论述了城市生活垃圾焚烧飞灰的组成特性及重金属的分布和性质,从飞灰熔融过程原理、重金属转化特性、重金属固化影响因素等方面阐述了熔融处理垃圾飞灰技术的研究进展,探究了飞灰组分和熔融条件对熔融过程及重金属固化效果的影响。论述了等离子熔融技术和熔融固化重金属的效果,最后对飞灰复配熔融及冷却过程优化处理给出参考性建议,并指出飞灰熔融处理技术未来发展方向。垃圾焚烧飞灰中重金属主要以其氧化物、氯化物、硫酸盐形式存在,熔融处理可以改变飞灰组分及相态,使飞灰发生多晶转变和熔融相变过程,重金属离子发生同晶置换反应,被固化在硅酸盐的Si—O四面体晶格结构中,很大程度上降低了飞灰的浸出毒性并实现熔渣资源化利用。熔融处理过程中,熔融气氛、时间及飞灰组分对过程特性和重金属的迁移转化影响较大,冷却方式不同会影响玻璃体熔渣的物理性质。根据重金属的熔点和沸点特性,在熔融处理后,烟气和二次飞灰中会携带部分挥发性强、沸点低的重金属。在今后研究中需要对烟气和二次飞灰进行冷却或二次捕集处理,并对烟气成分进行探究。由于熔融处理过程耗能大、投资高、关键设备研发难攻关,我国垃圾焚烧飞灰熔融处理技术仍处于技术研发阶段,尚无稳定化工业运行实例,但已有部分中试研究试验。熔融处理前,应先分析飞灰组成成分,根据飞灰组成进行预处理。通过添加助熔剂、调节飞灰碱度对飞灰进行复配熔融处理,降低熔融处理的能耗,高效稳定处理重金属。在实验室稳定有效试验的基础上,可以对等离子体熔融处理装置进行技术改进和创新,提高等离子火焰稳定性,实现熔渣的高效分离,提升装置耐久性。     

Manipulation of the ash flow temperature and viscosity of a carbonaceous Sasol waste stream

In 2001 Sasol investigated the possibility to convert a Sasol-Lurgi MK III fixed bed dry bottom coal gasifier at the former Sasolburg coal-to-liquids plant to a slagging gasification process and selected the Lurgi Multi Purpose Gasification (MPG) process for this purpose. At the time the MPG process was considered as a possible technology option suitable for the gasification of feedstocks which are difficult to manage, for example solid-liquid mixtures which are unsuitable for conventional solids or liquids processes and furthermore tars with a large variety of properties and high solids content have been gasified successfully.The most obvious differences between the feedstocks previously gasified, compared to the Sasol dusty tar, were found to be the viscosity and melting point of the dusty tar. The viscosity of the Sasol dusty tar mixture (as received) was higher than a factor of 10 of the previously used feedstocks. Another important feedstock property is the ash melting point of the feed within the gasifier. Ash particles fed with the tar melt in the high temperature zone of the flame. Molten ash particles, which hit the gasifier wall, will solidify and stick to the wall, if the wall temperature is below the melting point of the ash. The melting point of the dusty tar ash is 1380 °C and a fluxing agent has to be added to the dusty in order to reduce the melting temperature below 1250 °C to limit excessive wear of the refractory lining.Two approaches were evaluated in order to lower the viscosity, i.e. milling of the dusty tar and addition of low viscosity feedstocks to the dusty tar. It was concluded from this study that the viscosity of dusty tar can be decreased with the addition of specific waste solvent streams. The ash fusion temperatures of dusty tar can be lowered with the addition of a fluxing agent. The addition of spent Fe-catalyst as fluxing agent was also investigated, but was found to be not as effective as limestone. In some cases the addition of Fe can cause the acid/base ratio to change in such a way that the ash fusion temperature increases.In conclusion it can be highlighted that the ash flow temperature and viscosity of the Sasol dusty tar stream, and possibly other carbonaceous sources as well, can be decreased to acceptable values for slagging gasification applications. The results clearly show in both oxidizing and reducing atmospheres the Fe-catalyst was transformed into the slag melt as either Fe₂O₃ under oxidizing conditions and FeO under reducing conditions. The slag showed no sign of metallic Fe and was very homogeneous under oxidizing and reducing conditions. Spent Fe-catalyst can be discarded in a safe and environmentally acceptable way during high temperature gasification.     

电弧炉熔融医疗垃圾焚烧灰的实验研究

利用处理量为2 kg的直流电弧炉对医疗垃圾焚烧的底灰、底灰与布袋飞灰的混合灰分别进行熔融实验研究,并比较了熔融前后灰和熔渣的化学成分、物相、微观形貌、浸出毒性及重金属残留率. 结果表明,底灰主要由复杂的硅酸盐晶体组成,布袋飞灰含有大量的硬石膏(CaSO4)、氯化钠(NaCl)晶体,熔融后两种熔渣均为无定形非晶态的玻璃熔岩. 底灰、混合灰熔融后减容率分别达到78%和80.5%;熔融前布袋飞灰浸出液中Pb, Cd, Zn浓度远超过危险废物填埋限值,熔融后的熔渣中重金属固化在Si-O网格中,渗沥液中浓度极低,完全符合环保要求. 熔融后2种熔渣中Pb, Cd, Zn的残留率较低,而且混合灰熔渣中重金属残留率均低于底灰熔渣.     

煤焦气化反应过程中灰的熔融特性变化

抽样选出具有代表性的一种高灰熔点煤种和一种低灰熔点煤种,在TGA-51H型高温热天平上进行煤焦-O2、煤焦-CO2和煤焦-水蒸气气化反应实验,通过扫描电镜(SEM)考察了不同气氛下煤焦气化反应过程中高、低灰熔点煤灰的熔融变化过程,并利用EDX分析了灰的熔融机制。实验结果表明:同种煤样还原性气氛下的灰熔点比氧化性气氛下低;相同条件下灰在CO2气氛下的灰熔点比其在水蒸气气氛下低。在气化反应的过程中,由于气化反应为强吸热过程,大部分热量提供给煤炭气化反应,导致Ca与Fe元素的还原反应进行缓慢,灰熔融温度比较高。     

The leachability of heavy metals in hardened fly ash cement and cement-solidified fly ash

The effect of mix proportion, leachant pH, curing age, carbonation and specimen making method etc. on the leaching of heavy metals and Cr(VI) in fly ash cement mortars and cement-solidified fly ashes has been investigated. In addition, a method for reducing the leaching of Cr(VI) from cement-solidified fly ashes is proposed. The results mainly indicate that: (1) either Portland cement or fly ash contains a certain amount of heavy and toxic metals, and the leaching of them from hardened fly ash incorporated specimens exists and is increased with fly ash addition and water to cement ratio; (2) the leachability of some heavy metals is greatly dependent on leachant pH; (3) when carbonation of cement mortars occurs the leaching of chromium ions is increased; (4) the amount of heavy metals leached from cement-solidified fly ashes depends more on the kind of fly ash than their contents in fly ash; and (5) with ground granulated blast furnace slag addition, the leaching of Cr(VI) from solidified fly ashes is decreased.     

Investigation of the high-temperature behaviour of coal ash in reducing and oxidizing atmospheres

The high-temperature behaviour of ashes from a suite of coals exhibiting a wide range of mineralogies has been investigated. Phase analysis of ash samples quenched from various temperatures under either a reducing (60% CO/40% CO₂) or an oxidizing (air) atmosphere was performed by Mössbauer spectroscopy, scanning electron microscopy (SEM)/automatic image analysis (AIA), and X-ray diffraction (XRD). It was found that significant partial melting of the ashes occurred at temperatures as low as 200–400 °C below the initial deformation temperature (IDT) defined by the ASTM ash cone fusion test. Melting was greatly accelerated under reducing conditions, for which the percentage of melted ash increased rapidly between 900 and 1100 °C, saturating at temperatures above ≈ 1200 °C. The observation of such phases as wustite (FeO), fayalite (Fe₂SiO₄), hercynite (FeAl₂O₄), and ferrous glass in samples quenched from 900 to 1200 °C indicates that ash melting in a reducing atmosphere is usually controlled by the iron-rich corner of the FeO-Al₂O₃-SiO₂ phase diagram. Ashes rich in CaS are an exception to this rule, for large quantities of iron sulphide are formed and the melting behaviour is controlled in part by the FeO-FeS phase diagram. Under oxidizing conditions, potassium appears to be the most important low-temperature fluxing element, as the percentage of glass in samples quenched from temperatures below 1100 to 1200 °C was proportional to the amount of the potassium-bearing mineral illite contained in the coal. Above 1200 °C in air, calcium and, to a lesser extent, iron became effective as fluxing elements; melting accelerated between 1200 and 1400 °C, and was near completion between 1400 and 1500 °C for most ashes. To retard ash melting, it is generally concluded that aluminium is the most desirable constituent of ash, whereas the most undesirable constituents are iron, calcium, and potassium.     

柱淋滤模式下生活垃圾焚烧炉渣中Cu2+和Zn2+浸出规律

垃圾焚烧炉渣是一种活性材料，在其储存、预处理及应用等过程与雨水频繁接触时，炉渣中重金属随着水域环境发生迁移和浸出现象。本研究采用连续柱淋滤试验装置模拟自然降雨，开展了0～5mm和5～10mm焚烧炉渣的动态淋滤毒性浸出分析，重点研究了pH和降雨强度对Cu²⁺和Zn²⁺的浸出影响。结果表明，动态淋滤过程中，淋滤液pH变化对Cu²⁺和Zn²⁺的浸出水平影响显著，且在酸性较强淋滤液作用下Cu²⁺浸出水平比Zn²⁺更强，与Ⅴ类地表水环境浓度限值对比，在整个淋滤时间内Cu²⁺浸出浓度严重超标，在炉渣工程应用时需预防相关的环境风险；原生炉渣粒径大小与重金属浸出水平无直接相关性，但是0～5mm细炉渣中可浸出Zn²⁺含量更高，这与细颗粒物中Zn赋存形态和可溶出态含量较高有关；淋滤强度对重金属浸出水平影响主要反应了动态淋滤过程液固比和水分运移速率情况，当较低淋滤强度时具有低液固比，溶出液中重金属含量较高。     

Comparison of the characteristics of bottom ash and fly ash from a medium-size (32 MW) municipal district heating plant incinerating forest residues and peat in a fluidized-bed boiler

In this study, the physical and chemical properties of bottom ash and fly ash originating from the co-combustion of biomass-derived fuels (i.e. wood chips, sawdust, bark, and peat) from a 32 MW fluidized bed boiler at a municipal district heating plant were investigated. Silicate minerals were predominant in the bottom ash and calcium minerals in the fly ash, with most of the inorganic nutrients and heavy metals being enriched in the fly ash. The enrichment factors for heavy metals in the fly ash varied between 0.2 for silicon and 16.3 for lead, and for plant nutrients, between 1.5 for phosphorous and 108 for potassium. However, all heavy metal concentrations in both the bottom ash and fly ash were significantly lower than the current Finnish limit for maximum allowable heavy metal concentrations for forest fertilizers, which came into force in March 2007. According to the particle size distribution, the mass loadings of heavy metals in the fly ash were more than 90% contributed by the smallest particle size fraction lower than 0.074 mm. In the bottom ash, between 83.6 and 91.9% of the mass loadings of heavy metals were contributed by the particle size fraction between 0.5 and 2.0 mm.     

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.     

铝厂污泥对低灰熔点气化型煤熔融特性的影响规律

研究了铝厂污泥在弱还原气氛下对福建建兴矿煤(JX)、永安矿煤(YA)和创宏矿煤(CH)熔融特性的影响,考察了添加铝厂污泥前后JX煤灰在不同热处理温度下的矿物组成变化. 结果表明,JX煤灰熔点低是1000℃以上形成低温共熔物引起的;加入铝厂污泥作为阻熔剂可提高JX煤灰的熔融温度,添加量达6%(w)时(以煤灰基计),可使JX煤灰软化温度提高到1250℃以上,满足气化炉固态排渣对灰熔点的要求;加入阻熔剂后,在1000℃以上JX煤灰内形成了莫来石,莫来石在灰渣中起骨架作用,并延缓低温共熔物形成,从而提高了灰熔点.     

煤灰流动性研究方法进展

随着煤转化工业对转化率和生产效率要求的进一步提高,煤的热转化过程更趋向于在高温高压转化器中进行。在高温高压的液态排渣燃烧炉和气化炉中,煤中矿物质完全熔融成熔渣形式再排出。对于采用液态排渣和水冷壁的气流床气化炉,要求煤灰熔融温度低于操作温度,熔渣黏度范围为2.5~25.0 Pa·s,且在操作温度范围内黏度随温度的波动较小,因此气化过程中煤灰的熔融性和黏温特性是影响熔渣流动的关键因素。笔者论述了传统灰熔融评价方法的发展过程,各国标准方法的原理都是通过被压实样品在升温过程中的形变来判断得出熔融温度,但仅靠熔融温度无法提供实现现代大型气化过程精细化控制所需信息,而对煤灰熔融过程的全阶段测试有助于更准确地指导实际生产。对比各国研究者对熔融过程的定性和定量研究表明,熔融温度中的变形温度并非煤灰开始熔融的温度,针对煤灰沉积、烧结等问题,熔融全过程测试提供的开始收缩温度和热力学计算预测的液相最初形成温度有助于更准确地预测煤灰可能产生沉积或烧结的温度。黏温特性的测试目前仍依靠高温旋转黏度测试法,该法耗时较长且流程繁琐,因此研究者更趋向于用更简便和省时的方法实现对适用样品的黏温特性的快速筛选。除了试验方法,模拟计算方法在煤灰流动性研究中的应用越来越普遍,通过热力学计算和分子模拟方法,能够获得试验难以测得的矿物质组成及熔体的微观结构变化,且分子模拟中非平衡分子动力学方法可更准确模拟复杂流体的剪切稀化过程,从而获得更接近试验值的黏度计算结果。采用非平衡方法提高了计算结果的准确度,但也增加了计算的复杂程度及所耗费的机时,且目前煤灰体系的计算模型选择不多,因此采用分子模拟方法应综合考虑体系的复杂度与计算结果的准确性。随着熔融过程研究的进一步深入和模拟计算方法的普遍应用,试验结果呈现的宏观性质变化机理将更易于通过微观结构变化来阐明,反过来也将有助于优化现有的模拟计算方法和参数。     

Effects of hydrothermal aging on SiC-DPF with metal oxide ash and alkali metals

The silicon carbide used to make diesel particulate filters (SiC-DPF) has a maximum temperature of use, which is not the melting point of the filter material itself but rather the eutectic melting points of the ash materials and alkali metals deposited on the filter wall. Chemical reactions between the SiC filter and the other materials, i.e. ash materials and/or alkali metals, decrease the filtration efficiency and catalytic reactivity of engine out emission. The objective of this study is to understand the effect of hydrothermal aging on the SiC-DPF, and on the SiC-CDPF (catalyzed diesel particulate filter) deposited with ash materials and/or alkali metals. Hydrothermal aging simulated for the extreme condition of uncontrolled regeneration in DPF is carried out by using H₂O at high temperature. The surface change of the SiC filter was characterized in terms of the geometric microstructure and metal composites of the filter by using the SEM-EDS, BET and XRD. The accumulated ash materials and alkali metals in the SiC-DPF were an admixture, and the SiC-DPF after-treatment system always contained H₂O. According to the results, H₂O in the after-treatment system can be regarded as an influential factor of SiC-DPF durability even though the SiC itself has a very high melting point. The regeneration temperature has to be controlled under a critical value to ensure the durability of SiC-DPF in the after-treatment system, considering the fact that large quantities of ash materials, alkali metals and H₂O components are included in the exhaust gas.     

MgO含量对高钠煤灰熔融特性的影响

为研究MgO含量对高钠煤灰熔融特性的影响,配制了不同MgO含量的高钠合成灰并对灰熔融温度进行了测试。利用FactSage 7.0提供的热力学数据库建立了SiO₂-Al₂O₃-Fe₂O₃-CaO-MgO-Na₂O多元体系,模拟不同MgO含量的高钠合成灰的熔融过程。使用X射线衍射（XRD）和扫描电子显微镜（SEM）对合成灰的矿物质组成及微观形貌进行了研究。结果表明,随着MgO含量的增加,灰熔融温度先降低后升高。当MgO质量分数由0增加到5%时,高温下灰中生成大量低熔点的透辉石,透辉石会与霞石等矿物质形成低温共熔体,导致灰熔融温度降低。进一步增加MgO含量,高温下灰中生成镁黄长石、镁橄榄石和镁硅钙石等高熔点矿物质,使灰熔融温度升高。二元相图和似三元相图的结果表明,全液相温度随MgO含量的变化趋势与灰熔融温度相同。对本研究中的煤种,当MgO质量分数为30%时,可以有效提高灰熔融温度并抑制熔融液渣的生成。     

垃圾焚烧飞灰水洗脱氯及重金属浸出特性研究

系统研究了机械炉排炉垃圾焚烧飞灰水洗过程中氯化物和重金属的浸出特性,并采用Visual MINTEQ模拟分析水洗液中重金属的存在形态。结果表明：飞灰中的氯主要以可溶性氯化钠（NaCl）、氯化钾（KCl）、氯化钙（CaCl₂）、碱式氯化钙（CaClOH）的形式存在,飞灰水洗浸出成分97%以上为氯离子（Cl^-）、钠（Na）、钾（K）、钙（Ca）,其中氯离子占比高达60%;重金属及其他成分的浸出量很少,不足1%。水洗对氯离子的去除效果非常明显,可达92%以上,但是重金属的浸出量极低。飞灰单次水洗最佳条件：液固体积质量比为6 mL/g,洗涤时间为10 min。Visual MINTEQ模型分析表明,pH是控制飞灰水洗液中铅（Pb）、铜（Cu）、锌（Zn）、镉（Cd）形态的重要因素,氯离子（Cl^-）对镉的形态分布也有着重要的影响。飞灰水洗液电导率与氯离子质量浓度具有极好的线性相关性,其可作为监测滤液中氯离子质量浓度变化的有效间接指标。     

Thermal treatment of municipal solid waste incinerator fly ash using DC double arc argon plasma

In this study, glassy slag was produced by melting fly ash samples without any additives in a thermal plasma reactor, the core of which was a DC double anode plasma torch. After vitrification, there was an obvious change in the microstructural and the mineralogical characterization, an excellent resistance against leaching of heavy metal ions and a significant decomposition rate (99.95%) of PCDD/Fs in TEQ in the produced slag. These results indicate that the thermal plasma vitrification is an alternative technology with high efficiency and energy to dispose MSWI fly ash.     

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。     

重金属螯合剂处理垃圾焚烧飞灰的稳定化技术

引言随着我国社会经济的发展、城市化进程的加快以及人们物质生活的提高,全国城市生活垃圾年产生量已达1.5亿吨以上,并以每年8%～10%的速率增加[1-3]。城市垃圾焚烧是我国垃圾处置的重要手段,在焚烧过程中将产生大量飞灰,飞灰产量与垃圾种类、焚烧条件、焚烧炉型及烟气处理工艺有关,一般约占被焚烧垃圾量的3%～5%。分析表     

不同气氛下Ca-Fe二元助剂改变高硅铝煤灰熔融温度的规律和机制

准格尔高硅铝煤灰熔融温度（AFT）高,易引发液态排渣气化炉排渣口堵塞问题,需添加助熔剂降低AFT。利用灰熔融温度测试仪研究了不同质量比CaO/Fe₂O₃（Ca/Fe）助剂的助熔效果,结合热机械分析仪、热重-示差扫描量热仪、XRD以及热力学计算对比分析了氩气气氛与弱还原气氛下Ca-Fe协同助熔机理。研究发现,弱还原与氩气气氛下,AFT均随Ca/Fe增加先降低后升高,在Ca/Fe=1/1时AFT最低,但弱还原气氛下Ca-Fe的助熔效果优于氩气气氛。不同Ca-Fe助剂煤灰在变形温度（DT）、软化温度（ST）、半球温度（HT）和流动温度（FT）时对应的收缩程度差异较大,并且氩气气氛下熔融温度范围（DT~FT）内灰柱的收缩速率显著高于弱还原气氛下的收缩速率。氩气与弱还原气氛下煤灰的收缩过程均可分为三个阶段,且其收缩程度依次递增,但弱还原气氛下第一、二阶段收缩程度较氩气气氛下高。进一步研究表明第一阶段的收缩主要以化学反应引起的固相烧结为主,第二阶段以初始液相形成的液相烧结为主,而第三阶段的收缩行为最终决定煤灰的AFT。高温矿物演化行为显示莫来石和钙长石单独存在时AFT很高,但两者可以与含铁组分形成低共熔物降低AFT,并且Fe²⁺可以促进低共熔物的形成,促使弱还原气氛下低共熔物的生成温度低于氩气气氛下的。     

不同气氛下Ca-Fe二元助剂改变高硅铝煤灰熔融温度的规律和机制

准格尔高硅铝煤灰熔融温度（AFT）高,易引发液态排渣气化炉排渣口堵塞问题,需添加助熔剂降低AFT。利用灰熔融温度测试仪研究了不同质量比CaO/Fe₂O₃（Ca/Fe）助剂的助熔效果,结合热机械分析仪、热重-示差扫描量热仪、XRD以及热力学计算对比分析了氩气气氛与弱还原气氛下Ca-Fe协同助熔机理。研究发现,弱还原与氩气气氛下,AFT均随Ca/Fe增加先降低后升高,在Ca/Fe=1/1时AFT最低,但弱还原气氛下Ca-Fe的助熔效果优于氩气气氛。不同Ca-Fe助剂煤灰在变形温度（DT）、软化温度（ST）、半球温度（HT）和流动温度（FT）时对应的收缩程度差异较大,并且氩气气氛下熔融温度范围（DT~FT）内灰柱的收缩速率显著高于弱还原气氛下的收缩速率。氩气与弱还原气氛下煤灰的收缩过程均可分为三个阶段,且其收缩程度依次递增,但弱还原气氛下第一、二阶段收缩程度较氩气气氛下高。进一步研究表明第一阶段的收缩主要以化学反应引起的固相烧结为主,第二阶段以初始液相形成的液相烧结为主,而第三阶段的收缩行为最终决定煤灰的AFT。高温矿物演化行为显示莫来石和钙长石单独存在时AFT很高,但两者可以与含铁组分形成低共熔物降低AFT,并且Fe²⁺可以促进低共熔物的形成,促使弱还原气氛下低共熔物的生成温度低于氩气气氛下的。     

钢渣-粉煤灰复合胶凝材料的试验研究

以钢渣、粉煤灰等固体废物,掺加少量的普通硅酸盐水泥、脱硫石膏,辅以适量化学激发剂,研制开发新型复合胶凝材料。试验表明,少量水泥能够有效地激发出钢渣-粉煤灰体系潜在的活性,单掺水泥的钢渣-粉煤灰体系最优配比为:钢渣/粉煤灰=6:4,水泥掺量为15%;对于复掺水泥和脱硫石膏的钢渣-粉煤灰体系来说,最优配比为钢渣/粉煤灰=6:4,水泥掺量为15%,脱硫石膏掺量为10%。合适的化学激发剂可以较好地提高复合胶凝材料的性能,复合胶凝材料在自然养护的条件下比标准养护条件下强度增长更快。